Inorganic Chemistry Principles of Structure and Re Activity John Huheey 4th Edition PDF

Inorganic Chem.
istrY
Principles of
Structure and
Reactivity
Fou rt h Edi ti on
James E. Huheey
Univnsity of Maryland
Ellen A. Keiter
&stern Illinois Univnsity
Richard L Keiter
Eastern 1//inuis University
HarperCol}jnsCollegePublishers
F"rgures from the followill& journals 11re cop)'f'iflht 10 to the American Chemical Society:
Ac:coun/S of Chemical Research, Chcmiml ond Enginuring News, Chemical R<'vin.s,
Inorganic Chemistry, Journal of tlrt! American Chemicul Soclel), Journal of Chemical
Education, Journul of Physical Chemistry, and Orgonometallics. Grateful
ackoowledgmenl is also siven to Acto Chemica Scundinavlco. Tile American
Association for the Advancement of Science, The American lnstitUie of Physics,
Angt!'Wandtt! Chemie, The Chemical Society. The International Union of
Crystallography . The Mineralogical Society of America, The National Academy of
Sciences, U.S .A.,
The Nobel Foundation of the Royol Aodemy or Science,
Sweden, ultscltrift fiir unorganisch<' 11nd allgcmcittt! O.cmie. and uitschrift fiir
Nut11r/orschung for the use of materials that are copyri&ht C to them . Individual
acltoowledgmenls are si11en on the pages where the material occurs.
About lhr Qwer
The crystal structure or b01fgsite. a recently discovered natural zeolite. is composed of
sodium. calcium, aluminum. silicon. hydc-ogen . and oxyaen. Its unique atomic structure
of ten and twelve rinp wu determined by J. J . Pluth and J . V. Smith. aeopflyskists at
the Univermy of Chicago. Modelif18 tools used to construct the cover photogJaph are
bein& devdoped in the Catalysis and Sorplion Project of BIOSYM
Inc .
San Diego, California. Stlucture of bo&Jsite courtesy of Pluth. J. J.; Smith, J. V. Am.
Min"ol. 1990, 75,
and computer &raPhic by John M. Newsam. BIOSYM
Tedlnologies, Inc.
Sponsoring Editor: Jane Piro

Project Coordination: Elm Street PublishinQ Services , Inc.
Cover Oesi&n: Kay Fulton
Cover Photo: Professor John M. Newsnm , BIOSYM Technologies, Inc.
Compositor. Better Graphics, Inc .
Printer and Binder: R. R. Donnelley &. Sons Company
Co11er Printer: Lehigh Press Lithosnophers
Inorganic Chemistry: Principks of Structurt! and Rcoclivil), Founh Edition

Copyright C 1993 by HarperCollins Collq.e Publishers
All rights reserved. Printed in the United States or America. No pan of 1his book muy
be used or reproduced in any munner whatsoever without wrillen permission. except in
the case of brief qUOCations embodied in critical anicles and reviews. for inronnation
address Harper{:ollins College Publishers. 10 East Slrd Street, New Yorl;. NY 10022.
Library ol Congress Cataloglna-inPubllcatlon Data
Huheey, James E.
lnorpnic chemistry: principles or structure and reactivity I
James E. Huheey. Ellen A. Keiter, Richard L. Keiter.
p.
em.
Includes bibliographical references and inde x.
ISBN ()..()6.04299S.X
I. Chemistry, Inorganic . I. Keiter, Ellen A . II. Keiter,
Richal'd L.
Ill. Totle.
QOIS1.2. H84
97 98 99
1993
12 11 10 9
923(1083
To Catherine, Cathy. Terry, Mercedes, Tlwifin, Irene, Alvin, Eric, and Lise.
Contents
Preface xi
To lhe Student xiv
Excerpts from tire Preface to the Third Edition xvi
Chapter 1
What Is Inorganic Chemistry?
Inorganic Chemistry. the Beginnings

Inorganic Chemistry. an Example 2
Chemical Structure of Zeolites and Other Chemical Systems 3
Chemical Reactivity 5
Conclusion 7
Chapter 2
The Structure of the Atom

Tile Hydrogen Atom
10
10
The Polyelecaronic Atom 20
Chapter 3
Symmetry and Group Theory 46

Symmetry Elements and Symmetry Operations 46
Point Groups and Moleculur Symmetry 53
Irreducible Representations and Character Tables S9
Uses of Point Group Symmetry 63
Crystallography 74
vi
Contents
Chapter 4
Bonding Models in Inorganic Chemistry: 1. Ionic Compounds 92

The Ionic Bond 92
Lataice Enagy 99
Size Effects 112
The Predictive Power ofThennochemical Calculations on Ionic Compounds 127
Covalent Character in Predominantly Ionic Bonds
Conclusion 134
ChapterS
129
Bonding Models in Inorganic Chemistry: 2. The Covalent

Bond 138
Valence Bond Theory 139
Molecular Orbital Theory 1:53
Electronegativity 182
Chapter 6
The Structure and Reactivity of Molecules 203

The SIIUCture of Molecules 203
Structure and Hybridization 220
Bond Lengths 232
Experimental Detennination of Molecular Structure 233
Some Simple Reactions of Covalently Bonded Molecules 237
Chapter 7
The Solid State 252

The Structures of Complex Solids 253
Imperfections in Crystals 263
Conductivity in Ionic Solids 266
Solids Held Together by Covalent Bonding 269
Solid-State Mate.-ials with Polar Bonds 276
Olapter 8
Chemical Forces 290

Internuclear Distances and Atomic Radii 290
Types of Chemical Forces 296
Hydrogen Bonding 300
Effects of Olemical Forces 307
Contents
Chapter 9
vii
Acid-Bose Chemistry 318

Acid-Base Concepts 318
Measures of Acid- Base Strength 33()
Hard and Soft Acids and Bases 344
Chapter 10
Chemistry in Aqueous ond Nonaqueous Solvents 359

Water 360
Nonaqueous Solvents 360
Molten Salts 374
Electrode Potentials and Electromotive Forces 378
Chapter 11
Coordination Cllemistry: Bonding, Spectra, and Magnetism 387

Bonding in Coordination CompOunds 391
Valence Bond Theory 391
Crystal Field Theory 394
Molecular Orbital Theory 413
Electronic Specua of Complexes 433
Magnetic Properties of Complexes 459
Chapter 12
Coordination Chemistry: Structure 472

Coordination Number I 4n
Coordination Number 2 473
Coordination Number S 479
Coordination Number 7 S03
Coord.ination Number 8 507
Higher Coordination Numbers S09
Generalizations about Coordination Numbers 511
Linkage Isomerism 513
Other Types of Isomerism S21
The Chelate Effect .522
\ viii
Contenls
Chapter 13
Coordination Chemistry: Reactions. Kinetics, and

Medlanisms 537
Substitution Reac1ions in Square Planar Complexes
538
Thermodynamic and Kinetic Slability 547

Kinetics of Octahedral Substitution 548
Mechanisms of Redox Reactions 557
Olapter 14
Some Descriptive Chemistry of tfte Metals
sn
General Periodic Trends 578

Chemistry of the Various Oxidation Slates of Transition Metals 580
The Chemi.stry of Elements Potassium-Zinc: Comparison by Electron

Configuration 582
The Chemistry of the Heavier Transition Metals 581
Oxidalion Slates and EMFs of Groups 1-12 588
The Lanthanide and Actinide Elements 599
Coordinal.ion Chemistry 60S
The Transactinide Elements 613
Chapter 15
Organometallic Chemistry 623

The 18-Eiectron Rule 624
Metal Carbonyl Complexes 630
Nitrosyl Complexes 650
Dinilrogen Complexes 653
Metal Allcyls, Carbenes, Carbynes, and Carbides 6SS
Nonaromatic Alkene and Alleyne Complexes 662
Me.tallocenes 669
Reactions of Organometallic Complexes 686
Catalysis by Organometallic Compounds 70S
Stereochemically Nonrigid Molecules 723
Conclusion 730
Chapter 16
Inorganic Chains, Rings, Cages, and Clusters 738

Chains 738
Rings 765
Cages 785
Boron Cage Compounds 789
Metal Clusters 807
Conclusion 819
Chapter 17
The Chemistry of the Halogens and the Noble Gases 824

Noble Gas Chemistry 82j
Halogens in Positive Oxidation States 837
Halides 848
Pseudohalogens 852
Electrochemistry of the Halogens and Pseudollalogero; 8S3
01apter 18
Periodicity 857
F"rrsa- and Second-Row Anomalies 858
The Use of p Orbitals in Pi Bonding 861
The Use (or Not) of d Orbitals by Nonmetals 866
Reactivity and d Orbital Participation 87S

Periodic Anomalies of the Nonmetals and Posttransition Melals 876
Chapter 19
The Inorganic Chemistry of Biological Systems 889

Energy Sources for Life 889
Melalloporphyrins and Respiration 891
Dioxygen Binding, Transport. and Utilization 895
Electron Transfer, Respiration. and Photosynthesis 911
Enzymes 919
Nitrogen Fixation 933
The Biochemistry of Iron 935

Essential and Trace Elements in Biological Systems 941
Biochemistry of the Nonmetals
953
Medicinal Chemistry 954
Surrmary 960
Postscript 960
..
-.
J1
C10111enls
Appendix A
The Literature of Inorganic Chemistry A-1
Units and Conversion Factors A-3
Appendix C
Atomic States and Tenn Symbols A-7
Appendix D
Character Tables A-13
Appendix E
Bond Energies and Bond Lengths A-21
Appendix F
An Overview of Standard Reduction Potentials of the

Elements A-35
Appendix G
Tanabe-Sugano Diagrams A-38
Appendix H
Models, Stereochemistry, and the Use of Stereopsis A-40
Appendix I
The Rules of Inorganic Nomendature A-46
Index A-78
Preface
I t has been twenty years sinc.e the senior author and Harper & Row. Publishers
produced the firsc edition of Inorganic Chrmi11ry: Principles of Structurr ond
tiviry. In that rime; (a) The senior author has become 20 year$ more senior; (b) two
new authors have joined the project ; (c) Harpet" & Row. Publishers has become
HarpetColtins Publishers; and. most important, (d) inorganic chemistry has continued
10 grow from its already lusty exJstence of tWO decadeS ago. It is becoming increasingly impossible for one person to monitor all areas or incxpnic chemistry. The new
BUthors bring to the book their
in coordillalion chemistry, organometallics,
and ph}'Sical methods, as weU as fresh viewpoints on 11 number of othCT topics.
NevCTLheless. the philosophy of the book remains unchanged; To bring to the readCT
die essentials of inorganic chemililry in an easily readable format with emphasis on the
fact that inorganic chemistry is an exciting field of research rather than a closed body
or knowledge.
We three authors brought very different undergraduate experiences to the teach
ing or inorganic chemistry and the
of this editio n. One of us received a B.S.
degree from a Ph.D. grantinG institution, one from a private non-Ph.D. liberal arts
college, and one from a public non-Ph.D. liberal ans college. We have taugtu undergraduate and ttr.lduate inorganic courses in a variety of sellings. When we sat down to
discuss the revision, there were a number of things that we agreed upon; (I) The book
would be substantially updated. (2) The material presented would continue to be
thoroughly referenced, and the references would continue to appear on the pages of
interest. A relevant reference would not be omitted just because it had appeared in
previous editions. (3) New illustrations, many from the original literature. would be
added. (4) A greater selection of problems. many of them new, would be provided.
Many problems would require library assistance, while others would cover the fundamental aspects of each topic . (S) A chapter on
would be added. (6) Solid
state chemistry would be given more emphasis. (7) T he kinetics chapter would be
more fully developed. (8) The descriptive and organometallic chemistry of the la nthanides and actinides would be included in the corresponding chapters for the
transition metals.
General consensus (among both a&nhors and users) comes more easily than
agreement on specifics. Our discussions of the symmet ry chapter are a good example.
AU of us agreed that the tcachioi! of symmetry consider.uions at most institutions had
xi
xii
Preface
for the most part been delegated to the inorg11nic chemists. But how much should be
taught, and how much should the remainder of the book depend upon this chap.t er'! AI
a minimum we believed that a good introduction to point groups was essemial . We
also wanted to include some character table applications but not so much that the
inorganic chemistry in the book couldn't be taught without it. Applications appear
here and there in the text but can be a voided if desired . The chapter, as completed, has
concentrated on familiarizing the student with many applications of symmetry as used
by the inorganic chemist, including spectroscopy and crystallograph y, without purpOrting to be a rigOrous exposition of the
We may anticipate an eventual consensus on the amount and place of symmetry in
the chemistry curriculum, but for now we have assumed no prior background in the
subject. We have thus tried to illustrate a wide variety of uses of symmetry without
delving deeply into the background theory. We hope that those new to the topic can
find a useful introduction to the application of symmetry to problems in inorganic
chemistry. On the other hand. those having previous experience with the subject may
wish to use this chapter as a brief review. And. recognizing that things are in a state of
flux. we have attempted to make it possible to study various topics such as orbital
overtap, crystal field theory, and related materi.aJ, as in the past, with minimal
reference to symmetry if dtsired.
Students using this book come from exceedingly diverse backgrounds: Some will
have had extensive experience in physical and organic chemistry. perhaps even a
previous course in descriptive inorganic chemistry. For many. however, this will be
the first contact with
chemistry, and some may have had only limited
experience with bonding theory in other courses. For this reason, the early chapters
present the fundamentals of atomic and molecular suucture from the inorganic chemist's perspective. The well-prepared reader
use these chapters as a brief review as
weB as mortar to chink between previous blocks ofknowled&e. The middle chapters of
the book present the "heart of inorganic chemistry , solid-state chemistry beyond
simple salts. acid-base chemistry in a variety of solvents and the gas phase. and
coordination chemistry discussed in terms of bonding, spectra. magnetism, structure,
and reactions.
In line wilh the philosophy of a t opical approach and flexible course content, the
last six chapters of the book are essentially independent of each other, and one or
more may readily be omiued tlepending on the inclination of the instmctor and the
time available.
The fourth edition, in its enhrety, works nicely for thai unfortunately rare beDst.
the two-semester course. But that means that it is b;ilanced and should work equally
well for a one-semester course- the instructor must pick and choose. We firmly
believe that it is more useful to pro vide a large numb11r of topics. wherein one can
select the topics to be covered, than to dictate a "minimum core." We hope the book
includes the topics that
instnlctOrs find essential. but we hope that it also includes
their favorite topics. It obviously includes ours. A solutions
that contains
answers to all en<k>f-c:bapter problems
the fourth edition.
We would like to thank our colleagues a t the University of Maryland at College
Park (UMCP) and Eastern Illinois University (EIU) wbo hnve helped in a multitude of
ways. Professor Huheey's colleagues who helped with previous editions are listed in
the "Excerpts from the Preface to the Thin! Edition'' (page xvi). 3nd their further help
is gratefuily acknowledged. In addition, we would like to thank Bryan Eichhorn
(UMCP). Wtlllam Harwood (UMCP). Marte McGuire <EIU). Robert Pilato IUMCP),
and Rinaldo PoJi (UMCP) for special help with this edition. We would also like to
Prefoc
lliii
thank colleagJJes in departments that we have visited o n sabbatical leaves: Fred

Hawthorne. Hero Kaeu. Charles Strouse. Joan Selverstone Valentine. and Jeff Zink
(University o f California at Los Angeles). and Oren Anderson, Gary Maciel . Jack
Norton. Tony
and Steve Straus (Colorado State University), We would also
like to thank the Chemistry Departments 111 UC LA and CSU , the Zoology Department
at Southern Illinois University. as weU as our own departments for making possible
sabbatical visits to take ad vantage of these resources.
We are grateful to Michael W. Anderson. University of Cambridge: Anthony
Arduengo, E. 1. du Pont de Nemours: B. Oubost. Pechiney Inst itute: Jacek Klinowski. University of Cllmbridge: John Newsam. BIOSYM Technologies: Joseph J .
Pluth, University of Chicago: Arnold L. Rheingold. University of Delaware:
P. Sainfort. Pecbiney Institute; Char101te L. S tem, University of Illinois, Urt>anaChampaign: Sir John Meurig Thomas. The Royal Institution of Great Britain: and
Scocl Wi.lson. University of Illinois. Urbana-Champaign. for special help with illustrations from their work.
The writing of this text has benefitted from the hdpful advice of many reviewers.
They include Ivan Bernal. Donald H . Berry, Patricia A. Bianconi, Andrew B.
Bocarsly, P. Michael Boorman. Jeremy Burden. Ben DeGraff, RusseU S. Drago,
Daniel C. Harris, Roald Hoffmann , Joel F. Liebman. John Milne. T errance Murphy,
Jack Pladriewicz, Philip Power. Arnold L. Rheingold. Richard Thompson. Glenn
Vogel. Marc Watters, James H. Weber. and Jeff Zink.
We began this preface indicating "changes" thnt have occurred in the last two
deode.s . We have dealt with new authorship and new inorpnic c hemistry above.
Con<:e.rning the merger of Harper & Row, Publishers. New York. and Collins, Publishers. London. t he entropy generated was quite unexpected. When the dust had
settled. there emerged t wo sterling performers: Jane Piro. Chemist ry Editor. and Cate
Rz.asa, Project Editor . who helped us in many ways. We are happy to acknowledge
o ur debt to them.
Finally, there are many. many faculty and students who have helped in the
original writing and further development of Lhis book. often anonymous in the brief
citation of colleagues and reviewers. They know who they are, and we hope they will
accept our sincere t hanks for a ll that they did.
James E. Huheey
Ellen A. Keiter
Richard L Keiter
To the Student
xiv
Once after a depanmenta.l seminar, an older professor was heard to remark that he
felt intimidated by all of the new theory and experimental spectroscopic me,t hods
known by the new chemistry graduates. A young graduate student was stunned; she
was sure it would take her years just to learn enough of the chemistry that he already
knew to get her degree. Meanwhile, two other professors were arguing heatedly over
the relative importance offacts versus theory. One said descriptive chemistry was the
most important because "facts don't change!"
"Well, some 'facts' seem to change-1 read yesterday that iridium is the densest
element; ten years ago when I was a student, I was told that osmium was the densest."
"They don't change as fast as theories: theories just come and gc; besides, what's
wrong with someone repeating an experiment and doing it better-gelling a more
accurate value?"
''That's the point; new theories are necessary to explain new experimental data.
and theories give us something to test, a framework around which we can dream . .."
"Dream! We need a little less 'inspiration' and a lot more perspiration. .. "
And so it goes.. .. These chemists and these arguments present a microcosm of
perpetual debates in chemistry and the essence of the great difficulty in writing an
upper level textbook of inorganic chemistry. The lield is vast: large numbers of
inorganic articles are published every week . New synthetic techniques allow the
isolation and identification of great numbers of highly reactive compounds. Theoretical descripcions have become increasingly sophisticated. as have spectroscopic
methods. Inorganic chemistry interacts with organic, physical, and even biological
chemistry. Borderlines between molecular and solid-state chemistry are rapidly disappearing. The older chemist may know many facts and theories but realizes it is only a
small portion of the whole. The new graduate, with well-developed skills in a few
areas, also has a sense of inadequacy. Perhaps the student faced with his or her first
advanced inorganic course feels this most acutely. The textbook for the course reflects
the instructor's choice of what portion of inorganic chemistry should be taught, what
mix of facts and theory, and what relative weight of traditional and new science.
Authors also make their choices and those are seen in the variety of available
textbooks on the market. Some are heavily factual, usually bulky, and especially
useful for finding out something about all of the principal compounds of a particular
element. Others present a blend of fact and theory but minimize the book bulk by
To the Student
liY
liAliting each topic to a few paragraphs. This has lhe advantage of including most
topics but the disadvantage of having to look elsewhere for a fuller development. Any
single book, of course. has this problem to a certain dqree, thus the need for many
references. Our book, Inorganic
Principlrs of
and
founh edition, is also a blend of fact and theory, but we think it is large enough for a
full meal. There is no reason to expect a book that deals wilh the chemistry of 109
elements to be smaller than a standard organic chemistry textbook!
We've enjoyed writing this book; we hope that you will enjoy reading il. If you do.
we'd like to hear from you.
James E . Huheey
Ellen A. Keiter
Richard L. Keiter
Excerpts from the Preface

to the Third Edition
I t has been my very good fortune to have had contact with exceptional teachers and
researchers when I was an undergraduate (Thomas B. Cameron and Hans H. Jaffe,
University of Cincinnati) and a graduate student (John C. B11ilar, Jr., Theodore L.
Brown, and RussellS. Drago, University of Illinois): and to have had stimulating and
helpful colleagues where I have taught (William D. Hobey and Robert C. Plumb,
Worcester Polytechnic Jnst.i tute; Jon M. Bellam11, Alfred C . Boyd, S11mueJ 0 . Grim,
James V. McArdle, Gerald Ray Miller. Carl l . Rollinson, Nancy S. Rowan, and John
A. Tossell, University of Maryland). I have benefitted by having had a variety of
students, undergraduate, graduate, and thesis advisees. who never let me relax with a
false feeling that I " knew it all." Finally, it has been my distinct privilege to have had
the meaning of research and education exemplified to me by my graduate thesis
advisor, Therald Moeller, and to have had a most patient and understanding friend.
Hobart M. Smith, who gave me the joys of a se<:ond profession while infecting me with
the "mihi itch." Professors Moeller and Smith, through their teaching, research, and
writing, planted the seeds that grew into t his volume.
Four librarians, George W . Black, Jr. of Sou thern Illinois University at Carbondale, and Sylvia D. Evans, Eliz.abeth W. McElroy, and Elizabeth K . Tomlinson. of the
University or Maryland, helped greatly with retrieval and use of the literature. I
should like to give special thanks to Gerald Ray Miller who read the entire manuscript
and proofs at the very beginning, and who has been a ready source of consultation
through all editions. Caro line L. Evans made substantial contributions to the contents
of this book and will always receive my appreciation. Finally, the phrase "best friend
and severest critic" is so hackneyed through casual and unthinking use. paralleled
only by its rarity in the reality, that I hesitate to proffer it. The concepc of two men
wrangling over manuscripts, impassioned to the point of literally (check Webster's)
calling each other's ideas "poppycock" may seem incompatible with a friendship
soon to enter its second quarter-century. If you think so, you must choose to ignore
my many trips to Southern Illinois University to work with Ron Brandon, to visit with
him and his family, to return horne with both my emotional and intellectual "batteries " recharged .
My family has contributed much to this book. both lllngible and intangible, visible
and (except 10 me) invisible . My parents have toteraled and
much over the
xvi
Excerpts " - the Prefoc:e to the Tllinl Editioo.
years, including love, support, and w:uchine their dining
11vii
become an impromptu
office; often the same week as holiday dinners. My sister, C:uhy Donaldson, and her
husband, Terry. themselves university tea<: hers, have both answered nnd posed
questions ranging from biology to chemical engineering. More important, they "have
been there" when I needed their unique help. To al of these go my deepest gratitude
and thanks.
James E. Huhecy
C h a p
e r
1
What Is
Inorganic Chemistry?
It is customary for chemistry books to begin with questions of this type- questions
that are usually difficult or impossible to answer in simple
definitions. Simple pictures, whether of words or of art, cannot portray all aspects
of a subject. We most recently had this impressed upon us when our editor asked
us to suggest some aspect of inorganic dlemistry for the cover of this book. The \'ery
nature of a co\'er implies a relatively simple, single item, such as a molecule, a structure, a reaction, or a property (or perhaps a simple combination of two or three of
these). Should we choose the structure of the new high-temperature superconductors
which recently gained a Nobel Prize for their d.iscoverers? You probably have read
about them in the popular press and wondered why "high
was colder
than a Siberian winter! Should we moose a metal "cluster compound'' that acts, at
the molecular level, like a microscopic fragment of the metal? How about an inorganic
molecule that is optically active (that's not a subject limited to organic chemistry).
or carboxypeptidase A (that's an enzyme, but interest in it is certainly not limited to
biochemists)? Maybe a symmetrical crystal of a compound like sodium thiosulfate,
photographer's "hypo," or a multicolor. polarized micrograph of an inorganic compound. But no single design can possibly portray the many, varied aspects of inorganic chemistry. In the same way, any short and simple definition of a complex
subject is apt to be disappointing and even misleading. So let's just try to see where
inorganic chemistry came from, what an inorganic chemist does. and, perhaps, where
the subject is going.
Inorganic Chemistry,
the Beginnings
The term inorganic chemistry originally meant nonliving chemistry, and it was that
part of chemistry that had arisen from the arts and recipes dealing with minerals
and ores. It began by finding naturally occurring substances that had useful properties, such as flint or chert that could be worked into tools (middle Pleistocene, ca.
S x 105 years ago or less). This search continues (see below). but now it is included
in the sciences of mineralogy and geology. Chemistry deals more with the changes
that can be effected in materials. One of the most important early reactions was the
1
I What h I n tganic Chemlal ry?
reduction of metal o11ides, ca rbonates, and sulfides to the free meulls:'
2Cu 2(0H).C0l
+ 2C
---+
4Cu
+ 4C01 + 2H1 0
( I . I)
[Copper/ Bronze Age, ca. 4500-7500 years ago)
Fel04
+ 2C
---+
3Fe + 2C01
(1.2)
[ Iron Age, from ca. 4500- 3500 years ilgO to preSent)

This was the first example of applied redox chemistry, but to this day the gain and
loss of electrons is central to inorganic chemistry. The terms
reduction, and
huse (from "basic metal oxide") are all intimately related to these early metallurgical
processes. [The term acid is deri\led from vinegar (L. acetum).]
Much of this early work was strictly pragmatic without any theory as we would
understand it. It was necessary to be able to identify the best and richest ores, to be
able to distinguish between superficial resemblances. The familiar properties of Joors
gold, iron pyrites, FeS1 , as compared with the element gold is a well-known example.
Some minerals such as the zeolites were poorty understood. The name comes
from the Greek words for boil ing ((tiV) and Stone (;.80<71 because. when heated, water
boils away from these minerals in the form of steam. How a solid Slone could also
be partly liq uid water was. of course, mystifying. The answer seemed to be of no
practical concern. so this queStion was relegated to
or
chemistry.
Inorganic: Olemistry,
an Example
Wanting to choose a single chemicnl system, somehow representutive of inorganic

chemistry, for our cover, we have picked a l'Jeolite. The term may not be ll!.miliar to
you. However. one or more :zeolites are almost certainly to be found in every chemical
laboratory, in you r home. and in many major industrial processes. They.
themselves. are the subject of chanica I research from structural determinations to
catalysis to the inorganic chemical aspec.ts or nutrition.
The particular zeolite illustrated on the cover is boggsi1e, a compound of sodium,
calcium, a luminum, silicon, hydrogen, and oxyt;en. It had been known for only a few
months when this book went to press.: Yo:t be1ween the Lime that 1he earliest observations were made on "boiling stones" I I 7S6) and the discovery of bo@gsite, other
zeolites had achieved mujor chemical imponancc. If your home hils a wutcr-softening
unit, it contuins :1 :zeolite or a related compouml.
Willer" contains mt:tal c.llions
that interfere with the actions of soaps and syn&hetic
Th.: ma1crial in the
water softener exchanges Na into the water. while removing M g! Ca! . and other
metal ions:J
( 1.3)
1 The fiBI chemical

such
the dilco,..ry d li rt. W<rc not oonsciously opplied 35 "arts :1.00
recipes" lh:u lo<.l 10
Pcrhops h olt/tsl conscious Applicolion d chemistry by
'"""'
I hal or lhc aaion or )'<:1$1$ un WJOf ;n b>ki"' oncJ brCWIII.. or the SOITICWMI leu wei dctin<d p<tlCCSS
orcook.ine.
It WllS discovcrcd along the ColumbO Riv<r, WIISI!inJion, by aroup

.,..nmotogists [Mo1Ta1.
A. Scfmu 1990. 141. 141); HoWIItd. 0 .
Tschctnich. R.
Smith, J. V:, Klein. G. L. Am. Minrrul.
1990, TS. 1200- 1204] and the struelurc delcrmincd 111 1he UniY<11ily or Chicaeo [rtUih. J. J:, Smith.
J. V. Am. Mtnnul. 1990. TS, 50t-501].
The symbol Z rqreseniS aU or 11 ZICdile structUR oc:cpl the ucllanaco ble Na "'""
What Js Jnooanic ChmlaJry?
This discovery was made in the 1850s. and it was the lin;t ion exchange water-softening
process utilized commonly. The ion exchangers used today in home softening units
are dosely related in structure ;md exchange properties. but are more stable for longterm use.
More recently, synthetic zeolites have made their appearance in a dosely
yet quite distioct, application. Not everyone, even in areas of quite ha rd water, has
a water softener. In an effort to counter the negative effects of hard water, manufacturers early adopted the practice of adding "builders" to soaps and synthetic detergents. At first these were carbonates ("washing soda/ and berates ("borax''}. More
recently, these have been polyphosphates, [0 3 PO(PO,)J'"- (m = n + 3). which complexed the hard water cations. that is, tied them up so that they did not interfere
with the cleaning process. The synthesis of polyphosphates and the study of their
chelating properties with Mg1 , CaZ+, and other cations, are other aspects of inorganiccbemistry. However, phosphate is one of the three main ingredients of fertilizer,4
and too much phosphorus leads to the eutrophication of lakes and streams. In an effort to reduce the nmount of phosphates used, manufacturers started using a synthetic
zeolite in detergents in the form of microscopic powder to adsorb these unwanted
cations. T oday, this is the largest usage of zeolites on a tonnage basis.
muttering, "So out with phosphate pollution, in with zeolite polLest you
lution!", zeolites seem to be one of the few things we can add to the ecosystem without
negative consequences. The very structures of zeolites make them thermodynamiclllly
unstable. and they degrade readily to more st11ble aluminosilicates that are naturally
occurring clays. But that raises other interesting questions: If they are metastable.
why do they form. rather than their more stable decomposition products? How can
we synthesize them?
Another use of zeolites has been as Mmolecular sieves." This very descriptive. if
slightly misleading, name comes from a remarkable property of these zeolites: their
ability to selectively adsorb molecules on the basis of their size. A mixture of gases
may be separated according to their molecular weights (sizes) j ust as a coarse mixture
may be separated by a mechanical sieve. Some chemistry labs now have Mexhaust-less
hoods" that selectively adsorb larger, noxious molecules. but are inert to smaller.
ubiquitous molecules such as water, dinitrogen (N 2 1, and dioxygen (0:). There are
zeolites that h11ve a special affinily for small molecules (like H 2 0) but exclude larger
molecules. They arc thus exa:llcnt drying agents for various labor.llory solvents.
Chemical Structure
of Zeolites and Other
Chemical Systems
Before we can understand how these molecular interactions em take place. we must
unden;tand the strucwres of zeolites. Important for at least a century, the use of structur.sl information to understand chemistry is more important now than ever before.
T he determination of chemical structures is a combination of careful experimental
technique and of abstract reasoning. Because we have seen pictures of
molecules all our lives in 1V commercials a nd company logos, it is almost impossible
for us to realize that it has not been long in terms of human history since arguments
were mude that such structures could not be studied (or even could not exist!) because
The crystallographer's ability to take
it was impossible to see atoms (if they
a crysllll in hand and to determine the arrangement of invisible atoms (Fig. 1.1) is a
Whon you buy un

"5-IO.S' fcrlilizcr, you arc buying nitrogen (5%. ClCprcsS<.<l as Nl. phosp.,uc
(10"1 .. expressed as P,O,). and powsium
ClCpressed as K10).
I Who I h horganh Chemlslry?
(c)
(xlB,OOO)
'--------'
501Jm
x400
2nm.
x7,200,000
(b)
(a)
F;g. 1.1 The slructuce d the synthelic zedbe ZSM-5: (a) microscOpic crystals; (b) nn
elecrron microgrdph of I he area nwtced in (a); (c) the crystal slnlCture of ZSMS rclued ro
the electron microgr:lpil. !Counesy of J. M. Thomas. Royallnsriture of Chemistry.!
triumph of abstraa reasoning. The determination of rhe slrucrurcs of molecules and
exrendcd structures is fundamental 10 the understanding of inorganic chemistry. It
is not possible to think of modem inorganic chemistry in terms of simple equations
such as Eq. 1.1 to 1.3: A three-dimensional view o f the arrangement of atoms is
necessary.
One of the unifying factors in the delermination of chemical structures has been
the use of symmetry and group theory. One has only to look at the structure of
boggsire to see thar it is highly symmetrical, but symmetry is even more basic to
chemistry than that. Symmetry aids the inorganic chemisr in applying a variery of
mer hods for the determination of structures. Symmetry is even more fundamental:
The very universe seems to hinge upon conccpls of symmetry.
The solid-state chemist and solid-state physicist have also developed other techniques for examining and manipulating solids and surfaces. Of particular inreresr
recently is a technique known as seonning tunneling microscopy (STM) which aUows
us to see and even to move individual atoms.' The atoms arc imaged and moved by
electrostatic means (Fig. 1.2).6 Allhough chemisrry is portrayed, correctly, in terms
of single atoms or groups of atoms, it is practiced in terms of moles (6 x 101 ' aroms).
mi llimoles (6 x 1010 atoms). or even nanomoles (6 x 10 14 a toms). seldom less. But
perhaps the horizon of atom-by-atom chemistry is not far away.
>Some: people: objc<:r 10 rhc usc ol tho verb "\o =-in I Iris
conccdy :HJui"' r!Qr sine< the w:ave
lcn&Jh of visible ti&hl is muc:h arcrcr t!Qn lhc otdtr o( m:ranirudc o( molecules, rhe latter eonnor be
seen dirCC1ly. but musr be dccrronic:ally im:l,..S. TNC. bur
h..wlredo of millions o( people
"see- I he Super Bowl on TV! What's tho cblfcrcncc?
6
EiaJer. 0 .
Scbw<izer. E. K. N01o1u l990, J4f, 524-526.
Whot h Ino rganic Chemistry?
(1)
(2)
Fig. 1.2 Scanning tunneling

or the mocment or xenon
adsorbed on l
mckcl surface. The nickel moms are not trnaged. Ench letter S nm from top 10 bouonl[Counesy ofO_M.
Chemical Reactivity
Although it is not possible for the chemist 10 absolute!)' co ntrol the movement of
individual a 10ms or molecules in zeolite struc1ures, the nature of the s1ructure itself
results in channels that direct the molecular mo1ioos (f ig. 1.3). Fu rthermo re., the sizes
and shapes of 1he channels determine which molecules c-.1n fo rm most readily. and
which can leae readily. A molecule that cannot leave !Fig. 1.4) is a pt to react further.
This may have important consequences: A cata lyst IZS MSl t hllt is structurally re
lil ted to boggsi tc is uS<!d in
alkylat io n of to luene by methano l to form
Th e methanol can provide methyl
to mukc all three (o rtho, mew . :tnd p:tra)
Fig. l.J Stereoview of tho: structure of bogg.site. Note the channels ru nning m the ct
di rection_ For help in sc.:in!l stereovtews, see
H. ( From Pluth. J J.; Smnh. J_V.
Am. M ineral. 1990, 75. 501- 507. Reproduced with permiSSIOn.)
t Whot is lnorgouc Che mistry?
Fig. 1.4 meta-Xylene (left) and ,..,a-xylene (right) an :1 channel in

synthclic zeolite
C3llliY$J ZSM S. (From Tbomas. J M Nlgew. CMn.. IN. Ed. Engl 1988. :!7, 1673 - 1691.
R"produccd with permission.]
xylene isomers. The

para isomer leaves readily (Fig. 1.5), but the angular
onho and meta isomers do not. They may react funher, that is. rearrange. and tf
para-xylene forms. it may then leave.'
In a related process, ZSMS may be used to convert methanol into a highocta ne gasoline. Petroleumpoor countries like New Zealand and South Africa are
currently using this process to produce g;uoline. If the production of para-xylene
and gasoline sounds too much like Morg:lnic chemistryh for t he introduct ion to an
inorganic textbook. it must be poi nted out th at there is a large branch of a:hemistry,
Ot,OHoFig. l.S llhtStr:uaon or shope sclcctivaty (Csocscry, S. M

Reproduced with permission. J
8r11 t911S, :!I. 473 - 477.
a "chcmic:d tweczcn" (STM ond n:latcd Ol'll"fOIUS) W< cl:um to cl'rect p:uticubr stercochcmic3J syntheses by
spcao!ly shaped uol1tes But tJ o.s toted that the&< spea-.Jly sh:apcd uolttcs
:uc alsn synthcsacd- wthout "ehemtc:al twecun".
Tht answer IS not as dtlficutt :u ot may Sm.
'So, in lieu
Whol Is Inorganic Che,..lshy?
C3lled Morganomemllic chemistry,M that

with an area intermediate between
inorganic and organic chemiSiry and broadly overlapping both. Both organic and
inorganic chemists wori< in organometollic chemistry, with the broad ge.neralization
ofien being that the products are
and mostly of interest to the organic
chemist, and the intermediates and catalysts are or more interest to the inorganic
chemist.
Zeolites may be used in purely inorganic catalysis, however. One reaction that
may be used to reduce air pollution from mixed nitrogen oxides,
in the industrial production of nitric acid is catalytic reduction by ammonia over :realilic catalysts:
(1.4)
The seriously polluting nitrogen oxides are thus reduced to two harmless molecules.
The strong bond energies of the dinitrogen molecule and the water molecule are the
driving for-ces; the zeolitic catalyst, in the ideol case, pl'OYides the pathway without
being changed in the process.
A related catalytic removal of NO from automobile exhaust may come about
from the reaction;
2NO
C:=:n
Nl + 0 1
(1.5)
using a Cu(l)/Cu(ll) exchanged zeolite ns a redox catalyst
or
or
To return to the problem the aenerat invisibility atoms, how does the chemist follow the course of a reaction if the molecules cannot be imaged? One way is to
use spectroscopy. Thus the conversion of methanol, first to dimethyl ether, then to
the higher aliphatic and aromatic compounds round in gasoline, can be followed by
nuclear
resonance (NMR) spectroscopy (Fig. 1.6). As the reaction proceeds.
the concentration of the methanol (as measured by the intensity or the NMR peak at
ppm) steadily decreases. The first product, dimethyl ether
ppm), increases at
first and then decreases as the aliphatic and aromatic products eventually predominate.
Conclusion
So why did we pick boggsite for the cover? Is it "the most important" inorganic compound known? Certainly not! It is currently known from only one locality and in
the form of extremely small crystal fragments.0 It is unlikely that it occurs anywhere
on earth in sufficient qunntities to be commercially important Yet its discovery adds
to cur knowledge of the stnctural possibilities of zeolites and the conditions under
which they form. And if we know enough about the structure of a material, we can
usually synthesize it if we try hard enough. The synthesis of zeolites has progressed,
though it must be admined that there is much yet to be understood in the process.
Boggsite is enough like ZSM-5. yet different. that it has anracted considerable auention. There is currently a massive effort in the chemical industry to try to synthesize
this very interesting material. 10 It may become an important industrial catalyst Then
again, it may not-only time will answer t/101 questiotL
lw.omooo. M.: Yuhiru. H.:T:>nda. K.: Nitunu. N. Mine. Y.: K:\I'Iwa. S.J.
t991 ,115.l7!7l1lll.
Pan olthe diffiatlty in determininc the ct)'1lal Slructlll't wa in poct<ifla OUl a suitable CI)Slal r,....,....,r
from the m:llrU In wbich iJ wao imbedded. Only one ...u loun4, OJ17 x O.OS x 0.16 mm in sire. Sec
FoolnOie 2.
10 Alper. J. Sd<n 1991,148, 1190- 1191.
Wht II tnoe ntc Chemistry?
As was pointed out at the begin ning of the chapter, many other subjects could
have been chosen for the cover: the new high-temperoture superconductors, metal
cluster compounds, an optically active inorga.nic molecule, a bioinorganic enzyme
(see how far inorganic chemistry has come from the days when it meant "non-living"'?).
or a crystal of photographer's hypo. Indeed, all of these !lave been used on the co1ers
of recent inorganic textbooks (one reason why we chose something different), a nd all
or them are as apprQpriate on the one h;md, and as limited in scope on t he other,
as boggsite. They will all be disCtJssed in the following chapters. U there is one thought
that you should take a way with you aner reading this chapter, and eventually this
book, it is the amazing diversity of inorsanic chemistry. It deals with 109 elements,
each unique.
It is thus impossible in n single chapter to do more than scrotch the surface of
inorganic chemistry: Structure, reactivity, cutalysis, thermodynamic stability, symmetry, experimental techniques; gas-phase, solution, and solid-state chemistry: they
are all part of the process. However, it is hoped that some idea of the scope of the
subject may have been formed. The followins chapters in this book attempt to provide the reader with sufficient basic knowledse of the structure and reactivit y of inorganic systems to ensure a more comprehensive underuanding. ll
" F a reCC111 fC"iew of
CAJalysis, .ce Thomas. J. M. Sci. Amrr. 1991. 166 !41. 112-tiB.
Chapte r
2
The Structure
of the Atom
A tomic structure is fundamental to inorganic chemisuy, perhaps more so even

than organic chemistry because of the variety of elements and lheir electron configurations that must be: dealt with. h will be assumed th01t readers will have brought
with lhem from earlier courses some knowledge of quantum mechanical concepts
such as the wave equation, the part icle-in-a-box, and atomic spectroscopy.
The Hydrogen
Atom
When the Schriidinger equation is solved for the hydrogen atom, it is found that
there are three characteristic quantum numbers n, /, and m1 (as expected for a threedimensional
The allowed values for these quantum numbers and their relation to the physical system will be discuss.:c.l below, but for now th.:y may be taken
as a set of thrl!e inteyrrs sp..-cifying a particular situation. Each solution found for a
different set of 11, /, and m1 is called an ttil/t'l!}im.-rion and represents an orbital in the
hydrogen atom.
In order to plo t lhe complete wave functions. one would in generlll require a
four-dimensional gro1ph with coordinates for each of the three spatial dimensions
(."(. y, z; orr, 0, 1/>) and a fourth value, the wave function.
In order t o circumvent this problem and also to make it easier to visualize the
actual distribution of electrons within the atom, it is common 10 break down the
wave function, '1', into three parts, each of which is a function of but a single variable. It is most convenient to use polar coordinates, so one obtains
'i'(r, IJ, 4>) = R(r) 8(0) Cl>(</l)

where R(r) gives the dependence of 'I' upon distance from the nucleus and
give the angular dependence.
10
(2.1)
and ell
The Hy olrogen A to m
The Radial Wave

Fun ction ,
11
T he mdiaJ func1ions for the first 1hrce orbi1als1 in the hydrogen a 1o m are
R
l sorbilal
11
= 2, I= 0, m1 = 0
2s o rbilal
11
= 2,1 = I, m1 = 0
2p orbital
ao
where Z is I he nudear charge, e is the base of na1ural logari1hms, lind is the radius
of I he first Bohr orbit According lo the Bohr lheory, this was an immu1able radius,
but in wave mechanics it is simply the "most probableK radius for the elect ron to be
located. hs value, 529 pm, is determined by a0 h1/4n1 me1 , where h is Planck's
constant and m and e are the mass and charge of the electron, respectively. In hydrogen. Z = f. but similar orbitals may be conslructed where Z > I for other elements.
For many-electron a 1oms, exacl solulions or the WolVe equation are impossible to
obtain, and these
orbitals are often used as a first approximation. 2
Although 1he radial functions may appear formidable. the importanl aspects
may be made apparent by grouping the constllllts. For a given atom. Z win be
constant and may be combined wi1h 1he 01her constams. resulting in considerable
sirnpliliauion:
R ., K ,,e- Z
Is orbital
n=2.1=0.m,=O
R= Kz.(2 - ::)eZI/lo
2sorbi1af
n = 2, I= I, m, = 0
R"' Kz,re ZttZ.
2p orbital
11
= I, I= 0. m1
T he mos1 apparenl feature of t he radial wave func1ions is thai they all represent a n cxponemial -decayK, and !hat for 11 2 1he decay is slower t han fo r n = I.
This may be generalized for all r.adia f functions: They decay as 11 .,...,..... For Ihis rcason, the r.ulius of lhc various orbil:l ls factually, I he most
rudius) increases
Wilh increasing II. A second feature is I he prc:sence o r a 1101111 in lhC 2s radial funCiion.
AI r 2aoJZ, R = 0 and the value of 1he radial func1ion changes from positive to
negative. Agai n, this may be generalized: s orbitals haven - I nodes, p orbi1afs have
n - 2 nodes, etc. The radial functions for the hydrogen 1.1', 2s, and 2p orbitals are
shown in Fig. 2. 1.
Because we are principally interested in the pmbllbility o r finding electrons at
various points in space, we shall be more concerned with the sq1wru or the radial
functions than with lhe functions themselves. It is the square of the wave funclion
1 The ccmpldc wave functions in lerms of Ihe quantum numbe11 " ond I ure siea by l':!ufing. L nw
N01u.- of 1/w CMmkfll 8-t. CorncU University. llhllc:l. NV, 1960 '" 1-6) ond Portcrlicld. w. W.
1-IJDftc Clwntiwy. A UllifiH Apptoocll;
R*ifla, MA. 1984 (n
of h)'<lroccn-likc Of1>;a.u for .....U;dectron AIOmJ IICJ)ccls clccl-ron repul!iooo. """ lhis
may oClen be o f<:riou< ooenimpliliallion I$CC P"8d 20-23).
llbe U5C
14
2 Th SJrvdute of lh Alom
3. In between, rand R both have finite values, so there is a maximum in the plot
of probability
as a function of r. This maximum occurs at r = a0 ,the
value of the Bohr radius.
Similar probability functions (including the factor 4nr2 ) for t he 2s, 2p, 3s, 3p, and
3d orbitals arc also shown in Fig. 2.4. Note tha t although the radial function for the
2s orbital is both positive (r < 2o0 /Z) and negative (r > 2ao/Z), the probability func
lion is everywhere posiliue (as of course it must be to have any physical meaning) as
a result of the squaring operation.
The presence of a node in the WdVC funaion indicates a point in space at which
the probability of finding the electron has gone to zero. This raises the interesting
question, MHow does the electron get from one side of the node to the other if it can
never be found exactly al the noder' This is not a valid question as posed. since it
presupposes our macrosoopically prejudiced view that the elearon is a particle. If
we consider the elect ron to be a standing wave, no problem arises because it simu ...
laneously exists on both sides of a node. Consider a vibrating string on an instrument
such as a guitar. tr the string is stopped at the twelfth fret the note will go up one
octave because the wavelength has been shortened by one..Juil[ Although it is experi
mentally difficuh (a finger is not an infinitesimally small point!). it is possible to !'Ound
the same note on either half of the octavestoppcd string. This vibration can be con
tinuous through the node at the fret . In fact. on the open Siring, overtones oocur at
the higher harmonics such thou
occur at various points along the string. Nodes
are quite common to wave behavior, and conceptual probk:rns arise only when we
try to think of the electron as a
particle with a definite position.
Does the presence of one or more nodes and maxima have any chemical effca!
The answer depends upon the aspea of bonding in which we are interested. We shall
see la ter that covalent bonding depends critically upon the overlap of orbitals. Con
ceivably, if one atom had a maximum in its radial wave function overlapping with
a region with a node (minimum) in the wave function or a second atom, the overlap
would be poor... However, in every case in which careful calculations have been made,
it has been found that the nodes lie too close to the nucleus to affect the bonding
nppreciably.
The presence of nodes and small
docs have a profound ef
feet on the enl!rgy of electrons in different orbitals. An electron in an orbital with
these subnodal maxima (particularly s orbitals with higher values of II) are said tO
be P<'lletruling. that is. they have considcrahle electron density in the region of the
nucleus. This is the fundamental reason for the ordering of the energy levels in poly
electronic atoms: Is, !.r, 2p. ls. 3p, etc. (see pages 20-221.
Angular Wave
Functions
The angular part of the wave function determines the shape of the electron cloud
and varies depending upon the type of orbital involved (s. p, d, or f) and its orien.
talion in space. However, for a given type of orbital, such as s or p,, the angular
wave function is independent of the principal q uantum number or energy level. Some
Specifically. 1hc OO#rlop illltgro/ is Ihe inl..,ul.

'1'a4r. or lhc two woc functions (Sec Eq.
Ihe node lhc produd will !" IO WO. ond Will have small ....UCS in
tqion or the node.
AI
Fig. 2.5 Angular pan
or
the wave function ror

hydrogen-like s cxbilals
(lel\1and p orbitals
Only tWO dimensions or
the three-dimensional
1\mction have been shown.
typical angula r funct ions are
Fig. 2.6
probability runction ror

hydrogen-like p orbitals.
Only two dimensions of
the three-dimensional
function h:lve been shown.
1=0,m1 =0
0ll = [ l/ (4n))ll 1
I= l,m1 = 0
0ll = (3/(411)) 111 oos 8
P: orbital
I= 2.m1 = 0
0ll "' (.S/(167!)) 111{3 oos1 8 - I)
d,, orbital
s orbital
The angular functions for the s and p, orbital nre iUusir:lled in Fig. 2.S. For an s
orbital. 0ll is indepenclerlt of angle and is of constant value. Hence this graph is
cira.rlar or, more property, in three dimensions-spherica l. For the p, orbital we
obtain two tangent spheres. The p. and p1 orbitals are iden tical in shape but are
oriented along the x a nd y axes. rcspective.ly. We shall defer
treatment of
the J orbitals (Chapter II) and f orbitals (Chapter 14) un til bond formation in coordination compounds is discussed, simply noti ng here that the basi<: angular function
for d orbitals is four-lobed and that for f orbitals is six-lobed (see Fig. 2.9).
We are most interested in the probability of finding an electron. a nd so we shall
wish to examine the function 0 1 CI>1 since it corresponds to the angular pan of '1
When the angula r functions arc squared. different orbitals chunge in different ways.
For an s orbital sq uarins causes no change in sh:tpe si nce th.: function is everywhere
the same: thus anot her sphere is obtained. For both p and 1/ orbitals, howcvu. the
plot tends to become more elongated (st.'C Fig. 2.6).
The mean ing of Fiss. 2.S and 2.6 is easily misinterpreted. Neit her one has any
direct physical meaning. Bot h are graphs of mathematical functions, j ust as Figs.
22 a nd 2.4 are. Bot h may be used to obtain information about t he probable dist ribution of electrons, but neither may in any way be regarded as a
of an orbi
tal It is an unfonunate fact that fuzzy drawings of Figs. 2S or 2.6 arc often presented
as
Now one can define an orbital in any way one wishes. corresponding to
'. ' 2 R. R 1 , EJCl>, or 0 1 ll1, but it should be realized that Figs. 2.2. 2.4, 2.5, und 2.6
are mathematical functions and drawing them fuzzily does rrm represent un atom.
Chemists tend to think in terms or electron clouds, a nd hence ': probably gives t he
best
-picture" of a n orbital. Met hods or showing the total probability of
finding an electron including borh radial and a ngular probabilities arc shown in Figs.
2.7- 2.9. Although eleclron density may be shown either by shading (Fig. 2.7) or by
contours of equal electron density (Figs. 2.8 and
only the latter method is quantitatively accurate.
16
2 The Slructure of Ihe Alom
,.
tal
cbl
Fig. 2J (a)
of the dec:aron density in 11 hyd rotenlike lp orbbal
compared wilh lbl chc dcctron density a>ntours ror 1he hydrogen-like 1p, orbitnl of carbon.
Contour values arc
to the elcccron density maximum. The XJ plane is a nodal
surface. The signs ( + and -) refer to those or the original wave function. (The contour
diagram is from Ogryzlo. E. A.; Porter; G. B. J.
Educ. 1963. 411, 2S!!. Reproduced
wi1h permission.J
Fig. 2.8 The electron

density comours for
hydrogen-like Jp, orbital
carbon. Contour values
arc relative 10 the electron
density m3ximu m. T he xy
plane und u sphere o(
radius S2 pm !dashed line)
urc nodal surfKCCS. The
signs ( + and - ) rcl'er co
those or the original wave
function. (The
diagram is from Ogryzlo,
E. A.; Poncr, G. B.
J. Cllm.. due. 1963, 40,
256- 261. Reproduced with
or
permission.)
The Hy4rogen Atom
17
(bl
(1)
(cl
(d)
I e)
(f)
,,,
Fig. 2.9 Angular wave functions of s, p, d, and f orbilals illustrating gerade and wrgerade symmetry: la) s orbital, yerude:
orbital, wtgerade; (c) pi<:torial representation of symmetry of p orbital; (d} d,.. orbilal, gerade; (e) pictorial
or symmetry or d orbital; (f) d,, orbilal, (/<!rode; (g) f., orbi1al, ungerode.
{b) p
Since > 2 cll 2 is termed an angular probability function. the question may properly be asked what its true meaning is. if not a
of electron distribution. Like
any other graph. it simply plots the value of a function (> 2 cll 2 ) versus the variable
(8 or 8, <J>). If one chooses an angle 8, the probability that the electron will be found
in that direction (summed over all distances) is proportional to the magnitude of the
vector connecting the origin with the functional plot at that angle.
Symmetry of Orbitals
In Fig. 2.9 are shown sketches of the angular

of the wave functions for s, p.
d. and f orbitals. The signs in the lobes represent the sign of the wave function in
those directions. For example, in the p, orbital. for 0 = 90, cosH"' 0 and for
90 < 8 < 2700, cos 8 is negative. The signs of the wave functions are very important
when considering the overlap of two bonding orbitals. ll is customary to speak of
the symmetry of orbitals as gerade or ungerade. These German words meaning even
and uneven refer to t he operation shown in the sketches-inversion about the center.
If on moving from any point A to the equivalent point B on the opposite side of the
18
2 The Slrudut'e of Jh Atom
center the sign of the wave function does not cllange. the orbital is said to be gernde.
The s orbilal is a trivial case in which the sign of the angular wnve function is everywhere the same. The d orbitals (only two of which are shown here) are also yernde.
The p orbitals. however, are unsymmetrical with respect to inversion and the sign
changes on going from A to 13; hence the symmetry is ungerade. Likewise, f orbitals
are 1mgerade. Another way of refe.r ring to the symmetry properties of these orbitals
is to say that s and d orbitals have a center of symmetry, and that p and f orbitals
do not. In addition to symmetry with respect to inversion about the center, orbitals
have other symmet.ry properties with respect to other symmetry operations. Tllese
will be discussed in Chapter 3.
It should be noted that most textbooks, including this one, generally portray
the symmetry of orbitals as in Fig. 2.9n-g with wnve functions plotted and the signs
marked. However, an exceedingly common practice in the original literature of both
inorganic and organic chemistry is to indicate the signs of the wave functions by the
shading of stylized orbitals. Fig. 29c indicates the symmetry of a p orbital and 2.9e
a d orbital by this convention.
Attention should be caUed to a rather confusing practice that chemists commonly use. In Figs. 2.7 and 28 it will be noted that small plus and minus signs appear.
Although the figure refers to the probability of finding the electron and thus must be
everywhere positive, the signs + and - refer to the sign of the original wave function, 'f', in these regions of space. In F ig. 2.8, for example, in addition to the inversion
resulting from the ungerade p orbital, there is a second node (actuaUy a spherical nodal
surface) at a distance of 6 aofZ resulting from the radial wave function. Although this
practice may seem confusing. it is useful and hence has been accepted. The '1'1 plot
is useful in attempting to visualize the physical upicture" of the atom, bul the sign
of 'f' is importam with respect to bonding.'
Energies of Orbitals
The energy levels of the hydrogen atom are found to be detennined solely by the
principal quantum number. and their relationship is the same as found for a Bohr
atom:
(2.5}
where m is the mass of the electron. e is the electronic charge, 11 is the principal quantum number, and Ia is Planck's constant. Quantization of energy and angular momentum were introduced as assumptions by Bohr, but they follow naturally from the
wave treatmenL The quantu m number n may have any positive, integral value from
one to infinity:
n = I, 2, 3, 4, ... , co
The lowest (most negative) energy corresponds to the minimum value of n (n

I)
and the energies increase (become less negative} with increasing n unt il the continuum is reached (n = co). Here the electron is no longer bound to the atom and thus
is no longer quantized, but may have any amount of kinelic energy.
The allowed values of I range from zero ton- 1:
1=0,1,2, 3, . .. ,n- I
See Orchin, M.: Jatre, H. H.: TIJ< lmporrun<e r{ AntihonJing Orbital.<; Houghton Mifflin: Boston. 1967:
pP S-9, for a good diswssion or !his poinL
The Hytlrogen At om
19
The quantum number I is a measure of the orbital angular momentum of the electron and determines the "shape" of the orbital. The types of orbitals are designated
by the leiters s. p. d.f. 11 .. corresponding to the values of I "" 0. I. 2. 3. 4 . . . ..
The firsc four letters originate in spectroscopic notation (see page 26) and the remainder follow alphabetically. In the previous section we have seen the various angula r wave functions and the resulting distribution of electrons. The nuture of the
angular wave function is determined by the value of the quantum number /.
The number of equivalent ways that orbitals can be oriented in space is equal to
21 + I. In the absence of an electric or magnetic field these orientations a.re degenerate;
that is. they are identical in energy. Consider, for example, the p orbital. It is possible
to have a p orbital in which the maximum elecuon density lies on the z-axis nnd the
:cy-plane is a nodal plane. Equivalent orientat.ions have the maximum electron density
along the :c- or y-axis. Applkation cl a magnetic field splits the degeneracy of the
sec of three p orbitals. The magnetic quantum number, m1, is related to the component
of angular momentum along a chosen axis- for example, the z axis- and determines
the orientation of the orbital in space. Values of m1 range from -/to + I:
m1 = -1, - 1 + 1, ... , - 1,0, +I, +2... , +I
Thus for I= I. m, = - I, 0, +I, and there are three p orbitals possible, p,, p,, and
p. Similarly, for I= 2(d orbitals),m, = -2. -I, 0, +I , +2, and for/= J(f orbitals).
m1 = -3, - 2,- I, 0, +I, +2. +3. 6
h is an interesting fact that just as the single s orbital is spherically symmetric.
the summation of electron density of a set of three p orbitals, five d orbitals, or seven
f orbituls is also spherical (Unsold's theorem). Thus. although it might appear as
though an atom such as neon with a filled set of sand p orbitals would have a "lumpy"
electron cloud. the total probability distribution is perfectly spheriCdl.
From the above rules we may obtain the allowed values of n, I, and m1. We have
seen previously (page 10) that a set of particular values for these three quantum numbers determines an eigenfunction or orbital for the hydrogen atom. The possible
orbitals arc therefore
n=l
n=2
n=2
n=3
n=3
n=3
n=4
1=0
1=0
I= I
1=0
I= I
1=2
1=0
Is orbital
2s orbital
m1 =0
m1 = -1, 0, +I
m1 = 0
2p,.,, .,1 orbitals

orbital
m1 = -1.0, +I
3p..,.,,.: 1 orbitals
m1 = -2, - 1,0, +I. + 2
, , .,.,
orbitals7
4sorbital
m1 =0
We can now summarize the relation between the quantum numbers n, I, and "'
and the physical pictures of electron distribution in orbitals by a few simple rules. It
Auhouah the p, and J,: crt>i- cO<TCSpOnll rom 0. then: is no $.,;1ar OMICH>n<
for
th<oCbcrorl>illllsundOih<:raluesofm . ThcfUIICtioMurccomplex form1 ;t I. 2andmust be formed inloncw.
lincur coonl*'niiO<IS for the real p and d orbiluls. See Moon:. W. J. Pfty>I<al
PrcntlccHall:
Englcwoo<ICIJITs, NJ.I972; p640:Atkins, P. W . Phyncu1Chnn1Siry,4lb.cd.; Freemon: S.U.Froncioco,l990:
p :162: Fis&i D. N . lntmrtivn ro LJ,cund PI.I.t.r; Wiley: New YO<t. 1964: pp 9-U.
'These orbituls an: skeiChcd
rurthct' in Chapecr II .
'\ 20
2 The Structure oil he Alom
should be emphasized that these rules are no substitute for a thorough under.;tanding
of the previous discussion, but merely serve as handy guides to recall some of the
relations.
I. Within the hydrogen atom, the lower the value of n, the more stable will be
the orbital. For the hydrogen atom, the energy depends only upon n; for atoms
with more than one electron the quantum number I is important as well.
2 The type of orbital is determined by the I q uantum number:
1=0, s orbitals
I= I, p orbitals
I= 2, d orbitals
1=3.
orbitals
1=4, g orbitals, etc.
3. There are 21 + I orbitals of each type, that is, one s, three p, five d, and seven
orbitals,
per set. This is also equal to the number of values that m1 may
assume for a given value of I,
m1 determines the orientation of orbitals,
and obviously the n umber of orbitals must be equal to the number of ways
in which they are oriented.
4. There are n types of orbitals in the nth energy level, for example, the third
energy level has s, p, and d o rbitals.
5. There are n - I - I nodes in the radial distribution functions of all orbitals,

for example, the 3s orbital has two nodes, the 4d orbitals each have one.
6. There are l nodal
in the
distributional functions of all orbitals,
for example. s orbital.s have none, d orbitals have two.
The Polyelectronic
Atom
With the exception of Unsold's theorem, above,

discussed thus far has dealt
only wirh the neutral hydrogen atom, the only arom for which the Schrodinger equation
can be solved exactly. This treatment can be extended readily to one-electron ions
isoelectronic with hydrogen, s uch as He, 2 , and Be3 +,by using the appropriate
value of the nuclear charge, Z . The next simplest atom, helium, consists of a nucleus
and two electrons. We thus have three interactions: the attraction of electron I for
the nudeus, the attraction of electron 2 for thC nucleus, and the repulsion between
dectrons 1 and 2. This is an example of the classic three-body problem in physics
and cannot be solved exactly. We can, however, approximate a solution to a high
degree of accuracy using successive approximations. For simple atoms such as helium
this is not too difficult, but for heavier atoms the number of interactions which must
be considered rises at an alarming rate and the calculations become extremely la.!'- number
of.
been used, but we
l'!ol ,
ore them !lere beyonJi
one of the more accurate
It is referred to,as_!lle
after the men wbo developed
it, or as the self-consistent field (SCF)
consists of (1) assuming a reasonable
wave function' for each or the. electrons 'in an-atom. except one,-(2) calcUlating the
effect which the field of
'or the electrons exert' on ihe'
:.t
..
;,
i !
lhe Pelyelechonlc Alom
21
chosen electron, and (3) calculating a wave function for the last electron, including
the effects of the field of the other electrons. A different elec!ron is then chosen, and
using the field resulting from the othu electrons (including the contribution from the
improved wave function of the formerly chosen electron), an improved wave function
for the second electron is calculated. This process is continued until the wave func
lions for all of the electrons have been improved, and the cycle is then started over to
improve further the wave function of the first electron in terms of the field re.sulting
from the improved wave functions of the other electrons. The cyde is repeated as
many times as necessary until a negligible change takes place in improving the wave
functions. At this point it may be said that the wave fu nctions are self-consistent and
are a reasonably accurate description of the atom.
Such calculations indicate that orbitals in atoms other than hydrogen do not
differ in any radical way from the hydrogen orbitals previously discussed. The prin
cipal difference lies in the consequence of the increased nuclear charge- all the or
bitals are somewhat contracted. It is common to call such orbitals which have been
adjusted by an appropriate nuclear charge hydrogen-like orbitals. Within a given
major energy level it is found that the energy of these orbitals increases in the order
s < p < d <f. For the higher energy levels these differences are sufficiently pronounced that a staggering of orbitals may result, such as 6s < Sd z 4f < 6p, etc. The
energy of a given orbital depends on the nuclear charge (atomic number) and differ
enl types of orbitals are affected to different degrees. Thus there is no single ordering
of energies of orbitals which will be universally correct for all elements.8 Nevertheless. the order Is < 2s < 2p < Js < Jp < 4s < 3d < 4p < Ss < 4d < Sp < 6s < .5d::::
4f < 6p < 1s < 6d < Sf is found to be extremely useful. This complete order is correct
for nc single element; yet, paradoxica lly, with respect to placement of the ourennost or
valence electron, it is remarkably accurate for aU elements. For example, the valence
electron in potassium must choose between the 3d and 4s orbitals, and as predicted
by this series it is found in the 4s orbital. The above ordering should be assumed to
be only a rough guide to the filling of energy levels (see "The aujbau principle", page
23. In many cases the orbitals are very similar in energy and small changes in atomic
structure can invert two levels and change the order of filling. Nevertheless, the above
series is a useful guide to the building up of electronic structure if it is realized that
exceptions may occur. A useful mnemonic diagram was suggested by Moeller9 (Fig.
2.10). To recall the order of filling, merely follow the arrows and the numbers from
one. orbital to the next.
rEiedron Spin and

,.,,.the Pauli Principle
As expected from our experience with a particle in a box, three quantum numbers
are necessary to describe the spatial distribution of electrons in atoms. To describe
an electron in an atom completely, a fourth quantum number, m,. called the spin
quantum nt1mber must be specified. This is because every electron has associated
with it a magnetic moment which is quantized in one of two. possible orientations:
parallel with or opposed to an applied magnetic field. The magnitude of the mag
netic moment is given by the expression
1-1 = 2.00_../s(s :!"' I)
, :
..,
.St
..
.g
_.
(2.6)
.J
. Pilar, F. L. I . Chm. Educ.

SS, 2-6. Seem, E. R. Ibid.
D. lnorg. CMm.
t80S-I&tl.
r,.: P'oerlool, K.;
' Moder,
Wiley. New Vorl<, 1952; p '17. '
M.
Vanquictenbome, L. G.;
;.
2 The Structure of Ihe Alom
Ag. 2.10 Mnemonic for

determining the order of
filling ci orbitals
(approximate). (Adapted
from Moeller, T. Inorganic
Cl.emistry; Wiley. New

York, 19.S2. Reproduced
with pennission.]
orbt1::sJJ are nor fdkd

en known d emeftl:s
lmJ.
where the moment (It) is expressed in Bohr magne.t ons ((eh)/(4run))' 0 and s =
The allowed values of the spin quantum number are !. For an atom with two electrons the spins may be either parallel IS= I) or oppoSed and thus cancel (S = 0).
In the Iauer situation the electrons are referred to as paired. Atoms having only
0) are repelletl slightly when pl:leed in a magnetic field and
paired electrons (S
are termed
Atoms having one or more unpaired electrons (S i< 0) are
stongly auructct.l by a magnetic field ami are tenned pctrttmugnetic.
Electrons having the same spin strongly repel each other and tend to occupy
different regions of space. This is a result of a fundamental law of nature known as
the Pauli e:tclusian principle. It states that total wave functions (including spin) must
change their signs on exchange of any pair of electrons in the system. Briefly, this
means that if two electrons have the same spin they must have different spatial wave
functions (i.e., different orbitals) and if they occupy the same orbital they must have
paired spins. The Pauli principle and the so-called Pauli repulsive forces 11 have far10
In St the Bohr mogncton hu 3 vuluc d 9.27 >< 10 ,. with uniu of A m' or J T. '.
Pouli "force"' corresponds to no d:mic:ol inlcro<:tion bul ,...,Its from the nature d quontum ,..,.
chonics. All hough il i.! common in chcmi.!try 10 speak dMn:pulsions and "stabilizing cncrgicsM RSUtling
11 The
from the Pauti principle. lhese do not arise dim:dy from I he energtlics of spin-opin inlcroclioru bul
from the
cn..,.gy rC$Uitlng [rom I he spacial di$1ribution due to Ihe requirements o(chc Pauli
eutusion principle. Sec Kauunan. W. J.
ClvmiJtry; AC3dcmic: New York, 19S7; pp 1t9- 120;
Mat$Ctl, F. A. J . Am. Chm. So<. 1970. 92, JS2S-1S3&.
The Polyetectronlc Atom
23
reaching consequcn<:es in chemistry. For our present discussion the principle may be
stated as follows: In a given ocom 110 two electrons may haue all four quamum mtmlx!rs
idencical. This means that in a given orbital specified by n. I. and "'t a maximum of
two electrons may exist (m, = +t and rn, =
We can now add Rule 7 to those given on page 20:
7. Each orbital can contain two electrons, corresponding to the two allowed
values of m,:
The Aulbou Principle
t.
The electron conjiguracion, or distribution of electrons among orbitals. may be determined by application of the Pauli principle and the ordering of energy levels suggested
above. The method of determining the appropriate electron ron figuration of minimum energy (the ground sroce) makes use of the aufbau principle, or "'building up of
atoms one step at a time. Protons are added to the nucleus and eleclrons are added
to orbitals to build up the desired atom. It should be emphasized that this is only a
fonnalism for arriving at the desired electron configuration, but an exceedingly useful
one.
The quantum numbers n.l. and m1 in various permutations describe the possible
orbitals of an atom These may be arranged according to their energies. The ground
state for the hydrogen atom will be the one with the electron in the lowest orbital
the Is. The spin of the electron may be of either orientation with neither preferred.
We would thus expect a random distribution of spins; indeed. if a stream of hydrogen
atoms were introduced into a magnetic field, half would be deflected in one direction,
the other half in the opposite direction. Thus the four quantum numbers (tt,/, m,, m,)
for a hydrogen atom are (I. 0. 0. !).For the helium atom we can stan with a hydrogen atom and add a proton to the nucleus and a second electron. The first three
quantum numbers of this second electron will be identical to those from a hydrogen
atom (i.e., the electron will also seek the lowest possible e.nergy, the Is orbital), but
the spin must be opposed to that of the first electron. So the quantum numbers for
the two electrons in. a helium atom are (I, 0. 0, +!)and (I. 0. 0, -f). The Is orbital
is now filled, and the addition of a third electron to fonn 11 lithium atom
that
the :!.v orbital. the next lowest in energy. he used. The electron configurations of the
live elemo:nts tosethcr with the quantum numbers of the last electron areu
,Li
ts 2 2s 1
2,0,0.
4 Be
= ts 2 2s 2
2,0,0.
i
!
!
t
,B = ls 22s 2 2p1
2,1, '
ls'
1,0,0.
2
2 Hc = ls
1,0.0,
,H
This procedure may be continued, one electron at a time, until the entire list of elements has been rovered. A complete list of electron configurations of the elements
u The 111, 'lllucs for the unpaired dectroo in H. Li. and 8 aft'. or cour,.,, undc:finod and may be either
+for -i. II is mcrtly necessary thai the value$ for tho: second dearon cntcrins tho: sO<titol in He and
Be be opposite to 1hefirs1. Likewise.rho:lllst dcctron in boron mayenle< lho:p p,_or p,orbit;si..Uequol
in enet&Y, and so them, value given ubovc is arbi1r:uy.
24
2 The Shuclure ef the A l om
Table 2.1
Eleclt'Gn configura lions of

the elements"
z
1
2
3
4
6
7
8
9
10
ll
12
13
14
IS
Elem-
H
He
Li
Be
B
0
F
Ne
Na
Mg
AI
Si
p
s
a
16
17
18
19
20
21
Sc
22
1i
23
24
2.S
26
27
28
29
30
Ar
K
Ca
Cr
Mn
Fe
Co
Ni
Cu
Zn
Bectron ,
configuration
Bec!ron
Element
31 -Ga
ls1
lsl
(He]2s 1
(He]2s 2
(He]2sz2p'
(He}2sz2pz
[He)2s 22p4
(He}2s 2 2p'
(Hej2s 22p 6
(Ne]3s 1
(Ne}3sz
[Ne}3s 23p 1
(Ne)3s 1 3p 2
[Ne]3s 23p 3
[Ne}3s 2 3p 4
[Ne)3s 2 3p'
[Ne]3s23p6
[Ar)4s 1
[Ar)4s 1
(Ar}3d 14s1
(Ar}3d2 4s 2
[Ar)3d3 4s 2
(Ar}Jd' 4s 1
(Arlld'4s 2
7
32
33
34
35
36
37
38
[Ar}3d
(Ar}3d 8 4s 2
[Ar}Jd 104s 1
[Ar]3d 104s 2
Se
Br
Kr
Rb
Sr
39 y
40 Zr
41 - Nb "
42 Mo
43 Tc
44
Ru
45
Rh
40
Pd
47
Ag
Cd
48
49
In
so Sn
Sl
Sb
52 Te
53 I
S4 Xe
ss_. Cs
S6
4s 2
Ge
As
S7
S8
59
60
Ba
La
Ce
Pr
Nd
a>nfcguratiCn
[Ar}3d104s 24p 1
(Ar}3d 104s 24p 2
10
-'
I
[Ar]3d 4s 4p
[Arlld'o4s24p4
(Ar]3d 104s 14p'
(Ar)3d'04sZ4p6
(Kr]Ss 1
(Kr}Ss 2
[Kr)4d 1Ss2
[Kr)4d 2.SS 1
- [Kr)4d 4Ss 1
[Krl4d'Ss 1
[Kr)4d'Ss1
[Kr)4d7Ss 1
[Kr)4d8 Ss 1
[Kr)4d 10
[Kr)4d 10Ss 1
[Kr)4d 10Ss 2
(Kr}4d10Ss 2Sp 1
[Kr}4d 10Ss 2Sp2
[Kr)4d 10Ss 2Sp3

[Kr)4d '0Ss 2 Sp4
(Kr]4d 10Ss 2Sp'
[Kr]4d10Ss 2Sp 6
(Xe)6s '
[Xe)6s 1 [Xe)Sd 16s1
(XeJ.4[ 15d6s 2
[Xe)4f36s 2
[XeW6s 2 .
.i
--I
is given in Table 21. It will be seen that there are only a few differences bet ween
t hese configu rations obtained experimentally and a similar table which might be
constructed o n the basis of the aufbau principle. In every case in which an exception
occurs the energy levels involved are exceedingly close toget her and factors not accounted for in the above discussion invert the energy levels. F or example, the (n- l )d
and ns levels tend to lie very close together when these levels are filling. with the lntter
slightly lower in energy. If some special stability anses, such as a filled or half ..filled
subshell (see page 27 and Chapter II ). the most' stable arrangement may not be
(n- l )dxns2 I n Cr a nd Cu atoms the extra stability associated with half-filled and
filled subshells is apparently sufficient to make the ground-state configuration of the
i.s olated atoms 3d 54s 1 and Jd 104s1 instead of 3d 4 4s1 and 3d94s1 , respectively. Too
much importance should not be placed on this type of deviation, however. Its effect
on t he chemistry of these two elements is minimal. It is true that copper has a reason
ably stable + I oxidation state (corresponding to
but the + 2 state is even
mOTe stable in most chemical environments. Fo r chromium t he most stable ion in
aqueous solution is Cr3 , with the Cru ion and the C r(VI) oxidation state (as in
The Pol yel echonic Atom
25
Tahle 2.1 (Continued}
Eleclr"" configurations of
lha alementsa
Beclron
:Element
62 ..sm
63 - Eu
64 ,pd
65 'Tb
!)6
Dy
67
'Ho
Er
Tm
Yb
.Lu
68
(/}
70
71
72
lif
73 Ta
74
w
Re
75
76
Os
77 . Ir
78
Pt
79 i Au
Hg
80
81
Tl
82 .Pb
[Xe}-4f'6.r2. (Xe}4/66sZ
(Xe}4/7 6.r 2
(Xe)4f7 5d 16s 2
[Xe}-4flo6sz
(Xe)-4fn 6s2
(Xe)4fl26s2
[Xe}4f136s 2
[Xe}-4{146s2
(Xe}-4f145d16s 2
[Xe)4/145d2 6s 2
(Xe]4f'5dl6.r2
[Xe}-4{14Scl46s 2
(Xe]4/'45ds6sz
(Xe]-4f'45d76s2
(Xe}-4{ 145d 96s 1
lo6s I
[Xe)-4{145d 106s 2
[XeJ-4f'sd'o6sz6p I
[Xe}-4f'5do6sz6pz
rxewSd
z
83
Elemenl
84
85
86
Bi
Po
At
Rn
87
Fr
88
89
Ra
Ac
Th
90
91
92
93
94
Pa
95
Am
Cm
Bk
Cf
Es
Fm
96
97
98
99
100
101
102
103
104
Np
Pu
Md"
No"
Lrb
Rfb
Elec!ron
confogurotion
1
(Xe]4/sd o6sz6p 6
(Rn}7s 1
lRn)7s 2
[Rn)6d 17s 2
[Rn)6d27s 2
[Rn)Sf,6d 17s 2
[Rn}5r6d 17s 2
[Rn)5/7.r 2
(Rn)5/'6d 1s 2
[Rn}5/ 117s1
[Rn}5/127s 2
[Rn)5/1"7s 2
(Rn)S/ 146d7s 2
14
[Rn}5/ 6d'1s 2
MOe, C. E.IonlliJiionPotentiols ond lonilDiion Limits Dmvftffr om the Anolyusof

OptitolSptro, NSRDSNOS 34; National Bureau ofStnnclarcls: Washington. DC. 1970.
Ill!: on
are from The Chef111stry oft he Actinide
Elements; Kau,J. J.;Seabo<J. 0. T.;Morss. L. R., Eds.;CllapmanandHaU: NewYort<,
1986;Vol.2.
Predicted configuration.
Cr6!-) reasonably stable; the Cr( l) oxidation stute is practically unknown. For both
CuZ+ and Crl+ (as well as many other transilion melal ions) ligand field effects in
!heir complexes (see Chapter II) are much more importan t in determining stable
oxidation states than are electron configurations.
I n the case of the lanthanide elements (elements 58- 71) and those immediately
following, the 5d and 4/ levels are exceedingly close. In the lanthanum atom it appears that the 57th electron enters the 5d level rather than the 4/. Thereafter the 4J
level starts to lill, and some lanthanides appear not to have any 5d electrons. Here
again, too much attention to details of the electron configuration is not rewarding
from a chemist's point of view-indeed it may be quite misleading. The difference
in energy between a 5d"+ 14/"' configuration and a 5d"4f'"+ 1 configuration is very
smalL For mnemonic purposes all lanthanide elements behave as though they had
an electron configuration: 6s 25d 14f"; that is. the most stable oxidation state is always
that corresponding to loss of three electrons (the 6s and 5d). T here are some other
",abnormalities" in the electron configurations of various elements. but they are of
minor importance from a chemical point of view.
12
2 The Structure ef the A t om
..,
MJO I
1.0
Fig. 2.2 Radial density

functions for n 2 for the
hydroaen alom. These
functions give the relative
electron densily (e pm- ') as
a function of distance from
the nucleus. They were
prepared by squarina lhe
wave functions
in
Fis . 2.1 .
"to-
...
0.5
1 0
I.S
1000 1200
1.0
o.s
:!0.0
o.z
""' 100
tO.O
s.o
O.l
1 1
400
600
100
IZ
0-1
o"'::;_zoo
_.___
..
2.0
t ..S
-;;
"
-II
Fig. 2.1 Radial pan of the hydroaen eigenfunctions for" I, 2. 3. [From Henbera. G.
Atomic S(Hctra and Atomic:
Dover: New Yorit. 1944. Reproduc:c:d wilh
permission.)
t.O
41MI I\Otl
lpntl
"lo-
..
.8
1.0
...j
I I
that provides the electron density or the probability of finding an electron at a po int
in space. There are two useful ways of doing this. The simplest is merely 10 square
the functions plotted in F ig. 2.1. We could therefore square the numbers on the o rdinates and plo t the same curves except that the negative values become posi1ive when
squared (Fig. 22). While this seems very simple, it provides us with the relative electron density as a func1ion of the radius. I! is imporlant to remember thai for s orhitols.
the maximum electron density is o/ the nucleus; all ot/1er orbitals l1uve zero e/ec1ro11
density at the nucleus.
A more common way of looking at the problem is to consider t he atom to be
composed of"layers" much like an onion and 10 examine the probability of finding
the electron in the
which extends from r to r + dr, as shown in Fig. 23. The
volume of the thin shell may be considered to be dY. Now the volume of the sphere is
y =4m-3
3
(2.2)
R2 dY- 4nrR 1 dr
(24)
(2.3)
0
200 400 600
(pal)
Consider the radial portion or the wave function ror the Is o rbital as plotted in
Fig. 2 1. When it is squared and muJiiplied by 4nr1 , we obtain the probability function
Th Hycfl'oge n AJe m
13
Fig. 2.3 Volume of :t shell

o( thickness
ur.
dV
dr
shown in Fig. 2.4. The essential features of this funaion

as follows:
I. At r 0, 4nrlR 2
zero.3
..
obeained qualitati\cly
= 0; hence the value o f the function at the nucleus
2. AI large values o f r, R approaches zero rapidly and hence 4nr R2 must approach zero.
xJO-.
40
)( to
40
)( ro"'
30
tOO
'lO
800
liO
..
7.:
"
70
x lo
70
r.O
r.O
tO
0
so
40
I 0
40
t l
JO
:!0
tO
0
:!00 400
800
(l)mt
lpml
(p Al)
Fig. 2.4 Radial I)C'Obability functions for n- I, 2, 3 for the hydrogen atom. The function gives the I)C'Obability of finding
the electron in a spherical shell of thickness drat a distance r from the nucleus. [From Her1eberg, G. Awmic Spectra and
Almu/c Structure; Dover: New York, 1944. Reproduced with pennission.J
NOIC that the malhenultical ronc:1ion &<>eS Ia WO because Ihe volume ol.thc incrcmenlat shell, dV, aocs
10 zero a1 r 0. As we have seen, however. thefe Is cleclron density l1l the nucleus ror s orbilals.
26
2 The Str'-lchne of I he Atom
Although the aufbau principle and the ordering of orbitals given previously may
be used reliably to detennine electron configurations, it must again be emphasized
that the device is a formalism and may lead to serious error if overextended. For
example, in the atoms of the elements potassium, calcium. and scandium the 4s level
is lower in energy than the 3d level . This is not true for heavier elements or for charged
ions. The energies of the various orbitals are sensitive to changes in nuclear charge
and to the occupancy of other orbitals by electrons (see ..Shielding.. , page 30), and
this prevents the designation of an absolute ordering of orbital energies. It happens
that the ordering suggested by Fig. 2.10 is reasonably accurate when dealing with
orbitals corresponding to the valence shell of an atom; that is, the energies 3d > 4s
and Sp > 4d are correct for elements potassium and yurium. for example. but not
necessarily elsewhere.
Atomic States,
Term Symbols,
ond Hund's Rule
It is convenient to be able to specify the energy, angular momentum. and spin multiplicity of an atom by a symbolic representation. For example. for the hydrogen atom
we may defineS, P, D, and F states. depending upon whether the single electron occupies an s. p. d, or f oroital. The ground state of hydrogen. ls 1 is an S state: a hydrogen atom excited to a 2p 1 configuration is in a P state; etc. For polyelectronic atoms.
an atom in a P state has the same total angular momentum (for all elecrrons} a.s a
hydrogen atom in a P Slate. Corresponding to states S, P, D. F, . .. are quantum
numbers L = 0, I, 2, 3, 4, ... , which parallel the I values for s, p, d,f, ... orbitals. 13
Likewise, there is quantum number S (not to be confused wit h the S state just mentioned) that is the summation of all the electronic spins. For a closed shell or subshell,
obviously S 0, since all electrons arc paired. Somewhat less obviously, under these
conditions L = 0, since all of the orbital momenta cancel. This greatly simplifies
working with states and term symbols.
The chemist frequently uses a concept known as multiplicity, originally derived
from the number of lines shown in a spectrum. II is rclatoo to the number of unpaired electrons and. in general, is given by the expression 2S + I. Thus. if S = 0,
the multiplicity is one and the state is called a singlet; if S = !. the multiplicity is
two and 1he state is a doublet; S = I is a triplet: etc. H und's nrlf! of
multi
plicity states that the ground state of an atom will be the one having the greatest
mullipli.:ity (ic.. the greatest value of St. Consic.lcr a carbon atom I=
We may isnore tho: clo,;ec.l
and 2?. The awo :!p electrons may be p-.tired IS 0) or
have par.!lld spins in different orbitals (S c I). Hurxrs rule predicts rhatahe Iauer will
be the ground state, thlll is, a triplet of state. It happens that in rhis state L
I. so we
may say that the ground state of carbon is 3P (pronouncec.l "triplet-P..). The '" 3 P" is
said to be the tum symbol.
It is convenient for many purposes to draw
diagr.sms of electron con figurations in which boxes represent individual orbitals. and electrons and their spins
are indicated by arrows:
l.r
l s2
2s 2
@) @)
2,Z
u Tbi.! is the rcvc:rse ol the hislorieal process. S. P, D. and F stales were obseiVIl<l spa:rroscopicully a nd
IUimcd a lter .twrp, prln<l,.,.
.. .. and (unt/omnto/ charoderislics or rho spcctru. t..ltct the symbols
s. p. J, and f were applied 10 orbira/s. The methods (or asceriJiining abc vurious pos.<iblc wtut:S or Lund
the dctctmination of tcnn symbOls. as well as the vencrol ropic olrbc coupling or orbital angular momenta and cleerron angular momenta, are given in Appendix C.
Such devi::es can be very useful for bookkeeping, providing pigeonholes in which
to place electrons. However, the reader is warned that they can be misleading if improperly used, especially with respect to term symbols.
Traditionally, Hund's rule has been explained by assuming that there is less repulsion between electrons in the high-spin state, stabilizing it. Yet we have seen that
electrons having the same spin are highly correlated and actually repel each other
more than electrons of opposite spin (page 22). However, because electrons of parallel spin avoid each other, they shield each other from the nucleus less and the
nucleus attraction is greater and dominates: The overall energy is lowered. 14
The extrn stability of parallelspin configurations is given by the exdrnn!Jt' tlleryy:
..
="N(N-1) K
L...
2
(2.7)
where N is the number of elearons having parnllel spins. Because the exchange
energy is a quadrat.ic function of N, it rises rapidly as the number of parallel spi ns
increases: 0
(N
= 1}, 2
(N
(N = 2), 6
= 3). Since the number of parallel spins
is maximized for filled a od half-filled subshells. t he exchange energy is responsible

for the S(Ka]Jed
of these configurations. u
Periodicity of the
Elements
For chemists working with severnl elements, the periodic chart of the elements is so
indispensable that one is apt to forget that, far from being divinely inspired. it resulted
from the hard worlt of countless chemists. True, the.re is a quantum mechanical basis
for the periodicity of the elements, as we shall see shortly. But the
of such
scientists as Mend eleev and the perspiration of a host of nineteenth-century chemists
provided the chemist with the benefi ts of the periodic table abo ut half a century before the existence of the electron was proved! The confidence that Mendeleev had in
his chart, and his predictions based on it, make fascinating reading. 16
The common long form of the periodic chart {Fig. 2 11) may be considered a
graphic portrayal of the rules of atomic: structure given previously. The a rrangement
of the atoms follows naturally from the oufbau principle. The various groups of the
chart may be c:lassified as follows:
bl1x:k
lA um/ IIA
I ltlrd 2) . tf!l! alkali m1d
alkaline ear1/r metals. These clements are ulso sometimes culled the "light
metals". They are characterized by electron configuration of ns 1 or llliz over
a core with a noble gas configuration.
I . Tile
2. The "d" block elements: "8" Groups (Columns J- 12), r/u: trwrsilion
Characteristically, atoms of these elements in their ground stutes have electron
configurations that are filling d orbitals. 11 For example, the first transition
series proceeds from Sc(4r3d1) to Zn(4s1 3d 10) . Each of these ten elements
stands at the head of a family of congeners (e.g., the chromium family, VIB,
t!l84, JIO, 480-481.

u Blake. A. B. J. Owm. &hlt. t93t, J8, J9J-l98.
Boyd. R. J. NtJiun
10
t Ekmt,..., 'llh cd.: Chcmic;J/ Educ..tlon Puhlishing:
See Weeks. M. E.; LeiccsJer, H. M. OiJ<oerry of

Easton. p A, 1968.
''There- problems with 111\y simple definition ortnnsition mo:tal." See the dloalssion under "Semanric:s.
28
2 The Struchue of t he At om
Principal
qu>ntum
number
ns
(11-1)4
---,
"
2 I
He I
Nonmetals
Li&ht metals
........ _
..Atcericao"- lA
IIA
(I}
Li
Be
II
12
Na
Ma
19
VIUA
Transilion metals
(18)
lilA
IVA
VA
VIA
(2}
(IJI
(14)
(15)
(16}
(17)
He
9
F
He
20
VIIIB
..---r----.
ttiB
IVB
VB
VIB
VII B
(3)
(4)
(51
(61
(7}
(I)
22
2l
24
2S
Cr
Mn
21
ll
14
AI
Sl
26
27
28
32
Ni
z,
)I
Co
29
Cu
30
Fe
4S
46
Pd
47
48
As
Cd
78
PI
79
Au
37
Rb
l8
39
40
41
43
Zr
Nb
Mo
44
Sr
Tc
Ru
Rb
ss
S7
La
72
Hr
13
74
Cs
56
Be
7S
76
Re
Os
87
88
&9
Ac
104
l OS
106
Unh
107
101
109
Uns
Uno
Une
Fr
Ra
Rr
Ha
!UO'MI) (Unpl
16
118
(12)
Sc
IS
18
(II}
Ca
(10)
42
(9)
8
0
lz
c.
33
VIIA'"7"
17
10
18
AI
Ce
As
Se
34
JS
8r
36
Kr
so
Sl
In
Sn
S2
Te
Sl
t
S4
Sb
80
81
8)
84
11
8i
Po
8S
86
Ha
82
Pb
49
Xe
AI
Rn
71
Posttnonslticn melala
(11-2){
Lanthanide
S&
series
Ce
ACliNole
series
90
Tb
S9
Pr
61
62
Nd
Pm
Sm
63
Eu
64
C4
6S
Tb
Oy
91
92
9)
94
Np
9S
97
98
Pu
Am
96
Pa
60
Cm
Bk
66
cr
67
Ho
68
69
70
Et
Tm
Yb
Lu
99
Es
100
101
Md
102
103
Fm
No
Lr
Fig. 2.11 Period ic cha.n of the elements.
3. The Mr block elements: l..onchanide and actinide elements. These two series
often appear with a or t in Group III B (3), but these elements do not belong
to that family. (Note that the transilion metals do not belong to group IIA (2).
which they follow.) The most common oxidation state for the lanthanides and
some of the actinides is + 3, hence the popularity of the 1118 (3) posilion. Because of their remarkable electronic and chemical properties they should be
set apart, but most periodic tables give no special numerical appellations to
these elements.
4. The "p" block elements: The nonmetals and posllronsition metals, Groups III A
to VII/A (Columns /3 to 18). This block of elements contains six families
corresponding to the maximum occupancy of six electrons in a set of p orbitals.
The classification between metals and nonmetals is imprecise, principally be
cause the distinction between metal and nonmetal is somewhat arbitrary,
though usua.lly associated with a
dividing line running from boron
to aslatine. All these elements (except He) share the feature of filling p orbitals,
the noble gases (VIllA and 18) having a completely filled set of p orbitals.
T" Polyeledronic Atom
29
It is possible to trace the aufbau principle simply by following the periodic chart.
Consider the elements from Cs(Z = 55) to Rn(Z = 86). In the elemenll> Cs and Ba
the electrons enter (and fill) the 6s level. The next electron enters the 5d level and
La(Z 57) may be considered a transition element. In the elements Ce through Lu
the electrons are added to 4/ levels and these elements are lanclumide or inner transition elements. Afier the 4f level is filled with Lu. the next clcarons continue to fill the
5d orbitals (the transition elements Hf to Hg). and finally, the 6p level is filled in the
clements Tl to Rn, in accord with Table 2. I. 1bc periodic chart may thus be used
to derive the electron configuration of an element as readily as use of the rules given
above. It should be quite apparenl. however, that the chart can give us back only
the chemical knowledge that we have used in composing it; it is not a source ofknowtedge in itself. It is useful in portraying and correlating the information that has been
obtained with regard to electron configurations and other utomic properties.
-!
.t
Semantics, History,
and Other
Questions
Some chemists would define transition metals strictly as those elements whose
ground state atoms have partially fiHed d orbitals. This excludes zinc from the first
transition series. One must admit that zinc does have several properties that distinguish it from
transition metal behavior: It forms a single oxidation state,
Znh, which is neither paramagnetic nor colored and which forms rather weak complexes (for its small size). etc.t 8 If we so exclude zinc, do we also exdude Cu +, which
is isoelectronic with Zn 2 +,and metallic copper, which also has a filled 3d to configuration? More impo_rtantly, if we exclude zinc and ill> congeners, cadmium and mercury,
from the transition metals, then to be logically consistent we must exclude the noble
gases from the nonmetals. Some chemists might favor this, but the point is made in
Chapter 17 that the separation of the noble gases from the halogens. which are in
some ways similar, impeded noble gas chemistry. Finally, to be intern:llly logical
lutetium would have to be removed from the lanthanides and lawrencium from the
actinides. t 9
Likewise, the designation of groups as" or "B" is purely arbitrary. Assignment
of all of the transition metals to a- groups has an internal consistency as well as
historical precedent. 20 Unfortunately, some periodic charts have used "A" and "B"
in an almost opposite sense. zt In addition, as a historical carryover from the older
"short form" chart, the iron, cobalt, and nickel families were lumped under the nondescript "VIII". This state of confusion Jed the I U PAC to recommend that the groups
18 Note I hal these same criticisms apply equally well to scandium (known only as the Sc)+,
JcJO. ion).
is, lhere would be only

lanthanides and oc.tini<l, just .. etimination or zinc, cadmium,
and mercury leavu only
lransition metol aroups, and elimination oC the noble pses, k:avn only fit
- 8J"OUP$ to c-ain the nonmetals and posJiranoition
The m11in diffic:uDy with any o( these SUI
'acstions is !ha!Jhey con1ndic:J tbe simple expecJalions Jhal the s-block should consist oftwo cJements. the
p-block should consist of six dements, the dblodt sllould consisl or len dements. anclthefblock should
consist oC louneen clemens.
19 That
JO
Fcrncfius. W. C.: Powdl. W. H. J . Clwm. Edlff:. 1981, .S9, S04-SOK.
11
Historically, North American and RuSlian periodic charts labeled the muin group clements us "A und
the traruition metals os "B". Most other Europc4n churts labeled the fiut seven groups on the left
alkaline ..rth. ond transition metals in the SCllndium, titanium, vunudium, chromium. and mang-Jnese
!amities) as "A" and the IIISt seven sroups on the right 1exduding the noble JO.SC.S) liS the "B" groups
(copper. zinc. boroo, carbon, nitroacn. oxygen. and fluorine families). Such amiMauity is anathema 10
the indexer and abstncJer.
30
2 The Slruc tur of the AI om
be numbered I to 18, le:f! to right, from the alkali metals (I) to Lhe noble gases
Howe\'Cr Lhis does remO\Oe some or the pedagogical value or a simple J- VIII system.
especially for use in introductory courses. On the other hand, a very logical question
can be raised: Why not a 1- 32 numbering system with the lanthanides and actinides
incorporated in a "super"-Jong form or the churl?
To be sure, the form of the periodic chart that is most useful depends upon the
use intended. For Lhe simplest chemistry, perhaps the original short-form may even
be best: It gives the maximum oxidation state for all the elements and reminds us that
it is no accident that perchlorate ICI04 ) and permanganate (Mn04 I are similar
strong oxidizing agen ts. On the other hand, for someone whose main interest is in
the symmetry of electron configurations and the periudic chart, perllaps a complete
1-32 chart is the best)2 The bosfc conclusions that your authors hove used for this
book are: (lithe periodic table is a tool; (2) it should ben useful tool. IIIJ/Il clumsy one:
(3) the usual "long form" of the chart with both .. American .. A-8 labels a nd 1- 18
JUPAC
is the best compromise at present (Fig. 2. 111.
In a similar vein. suggestions have been rn:lde th:u all trunsactinide dements be
named by a system that translates the atomic number into a btinized name with a
three-letten!) symbol that is a one-to-one letter equivalent of the atomic
Within Lhis scheme. rutherfordium IZ = 104) would become unnilquadium. Unq.
according to Lhe formula tm = I. nil = 0. and qtwd 4, and hahnium would become
unnilpentium. Unp. One cannot help wondering: If Lhe atomic number. atomic symbol. and elemental name must needs become completely redundant. why is " element
104.. thought 10 be inadequate for the
However. the lUPAC calls these
.. temporary names.. to be used until n suitable name em
upon. which. it is
hoped. will be chosen in the time-honored nwnner.
Shielding
The energy of an elect ron in an a tom is a function of z:/n 1 Since the nuclear charge
( atomic oumber) increases more rapidly than the: principal quantum number. one
might be led to expect Lhat the energy necessary to remove an electron from an atom
would continually increase with increasing atomic number. This is not so, as can be
The: ionization energies
shown by comparing hydrogen (Z I) with lithium (Z
" IC !his is numbered 1-ll. ill1mllalcly lhe some problem IIJ beli>rc :arises Jhtou,&h imub..,..,... =sc
or 1-18 nnd t-32 chuns. Docs COlumn 17 rcrcr IO F. Cl. 8r. IUid I. 01 Lu""" Lt'1 tS Jensen. w. B.
CMm. l!lw. N,.,., t!lll7, 6J(JJ), 2-3.1S1rona ocrsumenll con be l'nhllc ror
AU rtcm lo un
AU.C sy..cm. A logic:ll fbrm islhc UK or a Slcp-pyl';lmi.J.IS JcnJ<n, w. B. CtHnp. & Mull!. 1\ppl. t9tl6.
118 .JI1-St0.J Such a c;h;!n makes the Jogicol stol!illu: A " IIMlin arOOP dements". B "lrnnsitioo
ckmenu" . C " inncrtransioion
( " bnth:lniclcs
IICiillidcsJ, Howc-.:r 11\is ,...,. acttptona
lhe Nonh Amcricato c"""<tllions with roprcl t o A 01\d 0 . wiOch mAy not' be pelilically prxtical. And
ioulcJtcs ore &oin& to look askance II tJIIY r........ - or A lAd B. P<rllaps inlenwt inclusion or the laJ>lhaaidennd actinides is not !he end o( the sso.-y: If the wpenctimd&s'' discu>Sed in Cluoplc.r 14 life ever
discoven:d. a /ifry colu- chol\ could follow! The &lep pyrarnid would :acc:ornndUc this pouibility
..n1h the addition or one
" D"' layer.
:u Chou. J. l'wr Appl. Cll<m. t979. $1. JBI - lk.
> The reason l'or propooina a ch:>ntl<.
only
in the lt'Odilloo:ll WilY or,.,.,. ct..
mmls (j,c., livina tt.IJ option lllld honoriO lhc diiCOYCtU)is AraWI or two
( :x;&on<; (I) There
111o<r1c1 be some
WilY
clcmotots .,., ..., as yet
o( conc.
the 11CD11tic .........., do.. this unambipousty. (21 Then: is "" ;,..,_ ftllioNI rivalry ond o:Nwvini"'" in
lhc diSCIOWry these dcmmls. an inab;!My to.._.. claimed dilcoveries.. arolthc r.cruw the moiJcr
10
ldltbe.,..
ts
l'a1wps the CUITCftl pt<SCI>CC t!/4smnt
w lndq>mdcnl eu,..,.,...,. bbonlloria wia
iswc. See o11o Cluopl ... ,._
t,.,..,..
or
or
or
The PotyeJectrenlc AJem
31
are 1312 kJ mol - 1 (H) and 520 kJ mol - 1 (Li). The ionization energy oflithium is
lowet" for two reasons: (I) The average radius of a 2s electron is ueater than that
of a Is electron (see Fig. 2.4); (2) lhe 2s1 electron in lithium is repelled by the inner
core ls2 electrons, so that the former is more easily removed than if the core were no t
there. Another way of treating this inner core repulsion is to view it as "shielding" o r
"screening" of the nucleus by the inner electrons, so that the valence electron actually
only part of the total charge. Thus, the ionization energy for lithium corresponds to an effective nuclear charge of between one and two units. The mdial probability functions for hyd rogen-like orbitals have been discussed previously (Fig.
The bulk of the electron density of the ls orbital lies between the nucleus and the bulk
of the 2s density. The laws of electrostatics state that when a test charge is outside
of a ..cage" of charge such as that represented by the Is electrons, lhe potential is
exactly the same as though the lalter were located at the center (nudeus). In this case
the valence electron in the 2s orbital would experience a potential equivalent to a
net nuclear charge of one (Z* = 1.0). A charge which penetrates the cage will be unshielded and would experience a potential equivalent to the full nuclear charge,
= 3.0. This is not meant to imply that the energy of the 2s electron varies as it
penetrates the Is orbital. but that the energy is detennined by an effective nuclear
charge,
which is somewhat less than the actual nuclear charge, Z:
z,
z = z - s
(2.8)
where S is the shielding or screening constant.

As a result of the presence of one or more maxima near the nucleus, s orbitals
are very penetrating and are somewhat less shielded by inner-shell electrons than
are orbitals with larger values of I. In turn, lhey tend to shield somewhat better than
other orbitals. Orbitals with high I values, such as d and f orbitals, are much less
penetrating and are far poorer at shielding.
In a similar manner the radial distributions of 3s. 3p, and 3d orbitals may be
compared (Fig. 24). Although the d orbitals are "smaller" in the sense that the most
pro bable radius decreases in the order 3s > 3p > 3d, the presence of one node and an
intra nodal maximum in the 3p orbital and the presence of two nodes and two intranodal maxima in the 3s orbital cause them to be affected more by the nucleus. Henoe
the energies of these orbitals lie 3d > 3p > 3s as we have seen in filling the various
energy levcl.s previously.
In o rder to estimate the extent of shielding. a set of empirical rules has been proposed by Slater. 25 It should be realized that these rules are simplified generalizations
based upon the overage behavior of the various electrons. Although the electronic
energies estimated by Slater's rules are often not very accurate, they permit simple
estimates to be made and will be found useful in understanding related topics such as
atomic size and electronegativity.
To calculate the shielding constant for an electron in an np or ns orbital:
I. Write out the electronic configuration of the element in the following order and
groupings: (Is) (2s. 2p) (3s. 3p) (3d) (4s , 4p) (4d) (4/) (5s. 5p), etc.
2. Electrons in any group to the right of the (ns, np) group contribute nothing to
lhe shielding constant.
11 Sial..-. J. C. PAy1. Rn-. t930. 16, 57.
S2
2 The Slruct ure of the Atom
3. All of the other electrons in the (ns, np) group. shield the valence electron to an
extent or 0.35
4. All electrons in the n - I shell shield to an extent or 0.85 each..

5. All electrons n - 2 or lower shield completely; that is, their contribution is
J.OO each.
When the dectron being sh.ielded is in an nd or nf group, rules 2 and 3 are the
same but rules 4 and S become:
6. All electrons in groups lying to the left of the nd or n/ gro up contribute 1.00.
Examples
I. Consider the valence electron in the atom 1 N = 1s2z.r22p 3 Grouping of the
orbitals gives
2p) 5 S - (2 X 0.85) + (4 X 0.35) = 3. 10.
Z =
z - s = 7.0 - 3.1 = 3.9.
2. Consider the vaJenc:e (4s) electron in the atom 1 oZn. The grouped electron configuration is (ts)"{2s, 2p)8(3s, 3p)1(3d) 10{4s)1 S = (10 x 1.00) + (18 x 0.85) +
( I x 0..35) = 25.65.
= 4.35.
3. Consider a 3d electron in Zn. The grouping is as in example 2, but the shield
ing isS (18 X 1.00) + (9 X 0.35) 21.15.
z ., 8.85.
It can be seen that the rules are an auempt tO generalize and to quantify lhose
aspects of the radia l distributions discussed previously. For example, d and f electrons are screened more effectively (S .. 1.00) than s and p elect rons (S = 0.85) by
the electrons lying immediately below them. On the other hand, Slater's rules assume that all electrons, s, p. d. or f, shield electrons lying above them equally well
(in computing shielding the nature of the shielding electron is ignored). This is not
quite true, as we have set.n above and will lead to some error. For example, in the
Ga atom ( = .. .
the rules imply that the 4p electron is shielded
as effectively by the 3d electrons as by the Js and 3p electrons, con trary to Fig. 2.4.
Slater formulated these rules in proposing a set or orbitals for use in quantum
mechanical calculations. Slater orbitals are basically hydrogen-like but differ in two
important respects:
I. They contain no nodes. This simplifies them considerably but of course makes
them less accurate.

2 They make usc of z in place of Z, and for heavier atoms, n is replaced by n,
where for n = 4, n = 3.7; n - 5, n '"' 4.0; n = 6, n = 4.2. The difference
between nand n is referred to as the quantum defect.
To remove the difficulties a nd inaccuracies in the simplified Slater treatment of
shidding, Clementi and Raimondi 17 have obtained effective nuclear charges from
.. &cepJ
ror lbc Is O<bital roc which 3 Voll-e o( o.JO scans 10 work beuu.
E.; Raimondi, D. L J. Clttm. Plop. 1963, J8, 2686-l689.
n Clementi
The rolyeleclronlc AI em
33
self-consistent field wave functions for atoms from hydrogen to krypton and have
generalized these into a set of rules for calculating the shielding of any electron. The
shielding which an electron in the nrh energy level and lth orbital (S.,) experiences is
given by:
Sl
0.3(N"- I)+ 0.0072(N"' + Nlp) + 0.0158(N3,,p,4 + N.,.,,J
= 1.no8 + o.360J(N"'- 1 + N 2p) + 0.2062(N3..PA + N ..,.pl

Slp = 25787 + 0.3326(N2,- 1)- 0.0773N3 - 0.0161(N 3, + N..,)
S2,
- 0.0048N 34
+ 0.008SN 4 ,
(2.9)
(2.10)
(2.11)
+ 0.2SOI(N 3 , - I + N 3,)
+ 0.0778N.., + 0.3382N 31 + 0.1978N 4 P (2.12)
S3 , = 9.3345 + 0.3803(N 3 , - I) + 0.0526N4 , + 0.3289N3 + 0.15S8N 4 , (2.13)
(2.14)
S4 , = 15.505 + 0.0971(N4 ., - I)+ 0.8433N 34 + 0.0687N4 ,
Sl> = 8.4927
S 34 = 13.5894 + 0.2693(N 3 - I)- 0.1065N,.,
s., = 24.7782 + 0.2905(N
4, -
(2.15)
(2.16)
I)
where N., represents the number of electrons in the nl orbital. For the examples given
= 3.756.
= 5.965. and
above, the effective nuclear charges obtained are
Zt,. 34 = 13.987. The shielding rules of Clementi and Raimondi explicitly account for
penetration of outer orbital electrons. They are thus more realistic than Slater's rules..
at the expense, however, of more complex computation with a larger number of
parameters. If accuracy greater than that afforded by Slater's rules is necessary. it
would appear that direct application of the effective nuclear charges from the SCF
wave functions is not only simple but also accurate. Such values are listed in Table :!.2.
With the accurate values of Table 2.2 available, the chief justification of "rules".
whether Slater's or those of Ocmenti and Raimondi, is the insight they provide inlo
the phenomenon of shielding.
zt....,
The Sizes of Atoms
Atomic size is at best a rather nebulous quantity since an atom can have no well
defined boundary similar to that of a billiard ball. In order to answer the question,
"How big is an atom?'' one must first pose the questions, "How are we going to measure the atom?" and "How hard arc we going to push?" If we measure the size of a
xenon atom resting in the relatively relaxed situation obtained in solid xenon. we
might expect to get a different value than if the measurement is made through violent
collisions. A sodium ion should be compressed more if it is tightly bound in a crystal
lattice (e.g., NaF) than if it is loosely solvated by molecules of low polarity. The question of how hard we are going to push is particularly important because measuring
atoms is analogous to measuring an overripe grapefruit with a pair of calipers: The
value we get depends on how hard we squeeze. For this reason it is impossible to set
up a single set of values called "atomic radii" applicable under all conditions. It is
necessary to define the conditions under which the atom (or ion) exists and also our
method of measurement. These will be discussed in Chapter 8. Nevertheless, it will
24
2 Th Slruclure of lhe AI om
Table 2 .2
tffectlve nud.ar cha'll"
for elemenlo 1 Ia 36
Elemenl
H
He
Li
Be
B
N
0
F
Ne
Na
Mg
AI
Si
s
a
At
K
Ca
Sc
Ti
Cr
Mn
Fe
Co
Ni
Cu
Zn
Ga
Ce
As
Se
Be
Kr
1.000
- 1.688
2.691
3.685
4.680
5.613
6.665
7.658
8.6.50
9.642
10.626
11.619
12591
13.575
14.558
15.541
16.524
17.508
18.490
19.473
20.457
21.441
22.426
23.414
24.396
25.381
26.367
21.353
28.339
29.325
30.309
31.294
32.278
33.262
34.247
35.232
2J
1.279
1.912 .
2.576
3.217
3.847
4.492
5.128
5.158
6.571
7.392
2p
2.421
3.136
3.834
4.453
5.100
5.758
6.802
7.826
8.963
9.945
IG.961
8.214
9.020
9.825
10.629
tt.9n
11.430
12.993
14.008
12.230
15.027
13.006
16.()41
n .n 6
14.574
17.055
18.06S
IS.3n
16.181
19.073
20.07S
16.984
17.794
21.084
22.089
18.599
19.405 23.092
Z0.213 - 24.095
2Ul20 25.097
21.828 26.098
22.599 ' 27.091
23.365
28.082
24.127
29.074
24.888 3o.065
25.643
31.0S6
26.398
32.047
....--.
Ss
3p
--
...
3d
4p
'
2..507
3.308
4.066
'"4.117
4.903
4.285
4.886
5.642
6.367
.S.482
7,068
6.116
1.151
6.764
1.711J
8.680
8.658
9.602
1().34()
9.406
11.003
10.104
11.709
10.785
12.368
11.466
13.018
12.109
13.676
12.nB
14.322 13.435
4.961 -14Jl85
IS.S94
14.731
16.219
15.369
16.204
16.996
17.760
17.014
18,S96
17.850
19.403
18.705
20.218
19.S71
21.033 Z0.434
3.495
4.398
4.632
4.817
4.981
5.133
5.283
5.434
5.576
5.711
S.858
5.965
7.o67
8.044
8.944
9.758
IO.SS3
11.316
7. 120
8.141
8.983
9.7S7
10.528
11.180
11.855
12.530
13.201
13.878
15.o9l
16.251
17.378
18.477
19.559
20.626
6.222
6.780
7.449
8.287
9.028
9.769
be useful now to discuss trends in atomic sizes without becoming too specific at the
present time about the actual sizes involved.
As we have seen from the radia l distribution functions, the most probable radius
tends to increase with increasing n. Counteracting this tendency is the effect of increasing effective nuclear charge. which tends to contract the orbitals. From these
opposing forces we obtain the following results:
I. Atoms in a given family tend to increase in size from one period ( = horizontal
row of the periodic chart) to the next Because of shielding. z increases very
slowly from one period to the next For example, usiag Slater's rules- obtain
The Polyeleclronlc A.Jom
35
the following values for Z*:

H
1.0
Na = 2.2
Rb = 2.2
K= 2.2
Cs
T he result of the opposing tendencies of" and z is that atomic size inaeases
as one progresses down Group lA (I). This is a general property of the periodic
chart with but few minor exceptions, which will be discussed later.
2. Within a given series. the principal quantum number does not change. [Even
in the "long" series in which the filling may be in the order ns. (n- 1)</. np. the
outermost electrons are always in the nth level.] The effective nudear charge
increases steadily, however. since electrons added to the valence shell shield
each other very ineffectively. For the second series:
Li = 1.3
N
3.90
1.95
B = 2.60
4.55
F = 5.20
c = 3.25
Ne
5.85
As a result there is a steady contraction from left to right The net effect of the
top-to-bottom and the left-to-right trends is a discontinuous variation in
atomic size. There is a steady contraction with increasing atomic number until
there is an increase in the principal quantum number. This causes an abrupt
increase in size followed by a further decrease.
Ionization Enet"gy
The energy necessary 10 remove an electron from an isolated atom in the gas phase
is the ioui=a.iot energy (often called ionization potential) for that atom. II is the energy difference between the highest occupied energy level and that corresponding to
n = cc, that is, complete removal. It is possible to remove more than one electron.
and the su.cceeding ionization energies are the second, third. fourth. etc. Ionization
energies are always endothermic and thus are always assigned a positive value in
accord with common the.rmodynamic convention (see Table
The various ionization energies of an atom are related to each other by a polynomial equation, which
will be discussed in detail later in this chapter.
For the nontmnsition elements (alkali and alkaline earth metals and the nonmetals) there are fairly simple trends with respect to ionizat ion energy and position
in the periodic chart Within a given family. increasing n tends to cauliC reduced
ionization energy because of the combined cfTccts of size and shielding. The transition and posttransition clements show some anomalies in this regard. which will be
discussed in Chapters 14 and 18. Within a given series there is a general tendency
for the ionization energy to increase with increase in atomic number. This is a re
suh of the tendency for
10 increase progressing from left IO right in Lhe periodic
chart. There are two other factors which prevent this increase from being monotonic.
One is the change in type of orbital which occurs as one goes from Group IIA (2)
(s orbital) to Group lilA (3) IP orbital). The second is the exchange energy between
electrons ol' like spin. This stabilizes a system of parallel electron
because
electrons having the same spin tend to avoid each other as a result of the Pauli
exclusion principle. The electrostatic repulsions between electrons are thus reduced.
We have seen previously that this tends to maximize the number of unpaired electrons
(Hund 's principle of maximum multiplicity) and also accounts for the "anomalous"
behavior ofCu and Cr. It also tends to make it more
to remove the electron
from the nitrogen atom than would otherwise be the case. As a result of this stabilization. the ionization energy of nitrogen is greater than that of oxygen (see
2. 12).
Table 2.3
'lonnalion energies (MJ mol
Z
Elemenl
'1 . H
)"
IU
II
He
P:Yi9'
Rb'
VI
VUI
VII
IX
1.3120
' 2.3723 5.2504

Li L
. 0.5203 7.2981
l!e . .
0.8995 1.7571
_
.B
'
O.SO!J6 2.4270
.6 . c
1.0864 2.3526
N
1.4023 7..8561
.8 0 r
1.3140 3.3882
9 F
1.6810 3.3742
10 Ne
2.0807 3.9523
.. ' 11 Na
o.49Ss 4.5624
- : 12 Mg
0.7377 1.4507
. 13 AI
' 0.5776 1.8167
Si C "' .,: 0.7865 1.5771
' i:S P
.- 1.0118 1.9032
$ J6 s
. 0.9996 2.251
a _ _ um U!J7
'Ar , !' 1.5205 2.6658
K ?
'' 0.4189 3.0514
"t-20 Ca "
0.5898 1.1454
0.631
1.235
2 1 Sc
, 0.658
1.310
- 22 Ti
23 v
o.650
1.414
24. Cr
0.6528 1.496
' 25 Mn
0.7174 1.5091
";<r26 Fe
0.7594 1.561
<27 Co
0.758
1.646
,. 28 Ni
0.7367 1.7530
-::-29- cit - - 0.74:55 - 1:9579
30 Zn
. 0.9064 1.7333
G3 -4- O.S788 1.979
Ge
0.7622 1.5372
As
0.944
1.7978
Se
0.9409 2.045
Br
1.1399 2.10
Kr
1.3507 23503
'
IV
0.616
1.181
.. 0.660
1.267
- 0.664 - 1.382
o:6sso 1.558
t.. 1.472
0.711 -=--- 1.617
0.720 . r 1.744
0.805 1,875
2.074
To obtain values in
11.8149
!L
eledron volu, multiply
14.848r '21.0065
table V'aiues bY; 10.364.
3.6598 25.0257 32.8266 , -("
;:f
4.6205 6.2226 .,37.8304 =..47.T169-,_
_
..:.
4.5781
7.4751 9.4449 .:53.2664. '64.3598
5.3004 7.4693 10.9895 1'3.3264 71.3345 84.0777
6.0504 8.4077 11..0227 15.1640 .17.8677 92.0378 _106.4340
6.122
9.370
12178 15.238 '19.999
23.069
115.3791 131.4314
6.912
9.544 '13.353
16.610
20.'115 "''25.490 t 28.934
14l.3626
7.7328 10.540
13.628
17.995
.l; 25.656
3,1.643
35.462
2.7448 11.578
14.831
18.378
- 27.459
31.861'
38.457
3.2316 4.3555 16.091 - 19.785 ..,.23:'?86 i29.252 -'i--- 33.877
38.733 2912
4.957
6.m9 21.269 '25.397. i' 29.854 . 35.867
40.959
3.361
4.564
7.013
8.4956' ,.!27.106
31.670 1 36.578
43.138
3.822
5.158
6.54
1.o182 ;-.33.605
38.s98
43.962
3.931
5.771 ' 7.238
:- 13.8417
40.760
46.187
4.411
5.877
7.976 I
16.964
48.576
4.9120 6.474
8.144
\ 14.207
18.192
20.3849
2389
7.089
8.844 10.12 $') 13.32
15.31
17.370
21.741
2.6525 - 4.1746 - 9.513 - 11.517 tfl13.59
18.64
20.833
2.8280 4.5066
6299
J2.362l.n 4.489 -f. 16.760 .if 19.86
. 22.24
2.987
4.74
6.69
; !5.54 {) 7.82
.. 20.19
23.58
3.2484 4.94
6.99 _ 9.2 , .;,.u.sos
2 1.40
"''23.96
2.9574
5.29
7.24 9.6 fi
14.575 ; 22.678 25.29
3.232
4.95
7.67 -: _9.84
: IS. I 17.959 - 26.6
3.393
5.30
7.28 . lOA 12.8 . 1S.6 ' 18.6
21.66
3.554 - -5.33
- 7.71- -9.94
--r-16.0 - 19.2 - - 22.4 3.8327
5.73
7.97 : 10.4
129 :ft HiS
' 19.6
23.0
2.963
62
:.- ....
J ' .;. .,:, I
3.302
4.410
9.02 ;
t
2.7355 4.837
6.043
12.31 t ,l j ':' i l'
'! _.
2.9737 4.1435
6.59 : :7.883 , ;14.99
3.5
4.56
5.76
8.55
9.938
18.60
3.565
S.01
6.24
7.57
" 10.11
.12.2
22.28
26.74
.I ll .
14.5
u .80
.. 15.6
17.1
1.980
5.96
7.43 - :, '8.97
'18.4
14.11
12.4
t._.
2.218
3.313 1 7.86 ..
...
2.416
3.69
- 4.877
2.621
.4.477
S.91 .
2.850 , .
.. 2.747
'J
.i
JO
:!: ;
2.991
3.177
3361 ,.
',
2.3 (ContitWed)
r:
lofhotion ....gies (MJ mor')"
.I
1.1704
'.Ba
)A
0.3757
0.5029
- - o.s381
0.528
O.S23
. 0.530
0.536
0.543
0.547
0.592
0.564
0.572
0.581
0.589
0.5967
0.6034
O.S23S
Q.6S4
0.761
rv
.li
2.046
2.23
0.96526
1.067
1.047
1.018
1.034
1.052
1.8503
1.949
2.086
2.13
2.15
2.26
2.40
1.068
1.085
1.17
1.112
1.126
1.139
1.151
1.163
1.175
1.34
1.44
4.820
3.543
3.761
5.552'
3.900
5.790
3.97
4.00
5.953
4.11
4.24
3.84
1.99
2.11
2.20
2.20
2.19
2.284
2.415
4.12
4.22
2.022
4.36
2.25
3.21
4.00
4.10
4.11
6.046
6.101
6.249
6.413
5.990
6.169 6.282
6.313
6.328
6.445
6.596
.:
0.760
0.84
0.88
0.87
. PI
Au
Hg
1.7911
1.98
1.8097
1.9710
0.890 I
1.0070
O.S893
- Pb - --- 0.7155Bi
0.7033
_Po
3.30
2.878
1.4504 --3.0815
4.083
1.610
2.466
4.37
1.93
2.78
. 6.64
5.40
0.812
AI
Rn
Fr
1.0370
Ra
0.5094
Q.97906
Ac
Th
0.49
0.59
1.11
Pa
:f
1.17
0.57
0.59
0.60
0.585
0.578
0.581 : 't
>
:J 0.601 t:T,';t'. ,j,
0.608 . -
1,
. 0.619 t ' I .\o

I
IY
"",.
J ;
'1htl
-.
-,.
o.no
lr
IX
VI
3.10
8.62
38
2 The Slructwre of I he AI om
"
..
-+
lo
1440
+..
))60
-#-
F;g. 2.12 Relative orbital tner8ics of the eletnaliS hydrogen to sodium. Solid lines indic:ue
orbital
differ :IS 3 result or
Dashed lines
ionization energies. whim
Tchl. 2.4
Ionization
Molecule
(MJ .....,,
IVI
Mol.alle
IMJ mol- l,
leVI
CH3
CzH,
CH,O
CN
0.949
0.784
0.729
1.360
1.352
:50.86
1..503
9.84
8.13
1.S6
14.09
14.01
:58.9
IS.S8
NH 1
NO
1.07.5
0.893
0.941
1. 16S
1.254
I.SI46
11. 14
9.26
9.7.5
12.07
13.00
IS.697
co
CF3
N2
NOz
0:
OH
F:
Uas.S. G.;8anmess.J . E.;Lkbman.J. F. ; Holmes. J. L.;Lcllin. R. D.;Mallard, W.(;.;

J. Phys. Cltrm. R({. Dalo 1981.17. SupplcmeJlt I, 1-861.
The iOnization energies of a few groupS are known (Table 2.4). Although not
generally as useful as atomic values, they can be used in Born- Haber calculations
(see Chapter 4) involving polyatomic cations. such as NO and
They also provi<Je a rough estimate of the electron-do!Ulling or -withdrawing t endencies of groupS.
o;.
Ionization
Tbe e,lectrons that are lost on ionization are those that lie at highest energies and thet-efore require the least energy to remove. One rnisht expect, therefore. that electrons
would be lost on ionization in the reverse order in which orbitals were filled (see "The
Aufbou Principle"). Thet-e
tendency for this to be true. However, there are some
very important exceptions. notably in the transition elements, which are responsible
The Polyelectonic Atom
39
for the characteristic chemistry of these elements. In general, transition dements react
as follows:
ls:2s2 2p6 3s!3p6 3d"4s: A lorn
ls 2 2J!2p6 3s 23p6 3d"

Oiposi1ivc cacion
T his is true not only for the first transition series but also for the heavier metals: The
ns2 electrons are lost before the (11 - l)d or (11- 2)/ electrons. This gives a common
+ 2 oxidation state to transition metals. although in many cases there is a more stable
higher or lower oxidation state.
This phenomenon is puzzling because it appears to contradict simple energetics:
If the 4s level is lower and fills first. then its electrons should be more stable and be
ionized last, shouldn't they? One might ask if there is a possible reversal of energy
levels within the transition series. If the relative ene'l!ies of the 3d and 4s levels are
examined, it is found that they lie very dose together and that the energy oC the 3</
level decreases with increasing atomic number. This is often advanced as the explanation for the electronic configuration of Cu. If the 3d level has dropped below the 4s at
atomic number 29,then the ground state must be 3d104s 1 Nevertheless. this can have
no effect on the phenomena that we are investigating. because we are inquiring as to
the difference in configuration between ground state of the neutral atom and the ionic
states of the same element. Because llll of the transition metals in the first series (with
excepeion of Cr and Cu) have a 3d"4s 2 ground state for the neutral atom and a stable
3d"4s0 state for the dipositive ion. the source of our problem must be sought in the
difference between atom and ion. not in trends along the series.
Before the question can be answered adequa tely. it is necessary to oJcfine what is
meant by Morbi tal energy". For most purposes. that given by Koopm<tns' theorem is
adequate: If the nth orbital is the highest orbital used tO describe the
wave function of an atom X. then the energy of orbital n is approximated by the ionization energy of the atom. These energies can be calculated by the
method described previously (see page 20). These cak:ulations have been made and
much has been written concerning their
The seeming contradiction
presented by the ground state of the atoms and the ground state of the
rc.sult.s
from the fact that it is the total energy of the atom (ion) that is important. not the sinsk
energy oft he electron entering the 4s level. We arc reminded again that dcctrons interact with each other in different ways depending upon their spatial distribut ion.
When nl/ of tire euer11ics a re summed, induding ((I/ of1/Je l!lt!L"Irmr-ehnmu
it is found that the [Ar] 3d"4s1 configuration is lower in energy than the (Ar] 3t/"-'4s!
configuration; or for the more common +2 ion, (Ar) 3d"4su < (Ar]
Unfonunately. this does not answer our original question completely. for we
cannot simply say that 4s electrons ionize before the 3d electrons because the 4s orbital lies higher in energy- we have seen tha t we must inspect the tOtal energy. One
could postulate (incorrectly) that because of electron- electron repulsions the correct
configuration for Ti2+ was (Ar] 4s 1 instead of ( Ar] 3<tl, which runs counter to experimental facL In order to account for the apparent change in stability. depending
on whether the 4s or the 3d orbital occupied. we must compare the two systems
involved, Ti versus Ti 2 . or more genemlly, M versus M 1 . A clue may be sought
10
Pilar. F. L J . Clwm. Educ. t978. SS. 2-6. Socrri.. E. R. Ibid. t989. 611. 48t-4lll. Vonqui<:kenbomc:. l. G.;
Piorlool.
Dc110sJ>c1. 0 . /ltOI"g. Clorm. 1989. 1JJ. t80S- 181l.
40
2 .. The Shuclure of lh Atom
from the trend along the Jd series mentioned above. Al!hough this trend is not responsible for the effect (as discussed previously), it does give an indication. h thus
appears that as the atomic number goes up, and hence as
increases, the energy
levels approach more closely to those in a hydrogen atom, namely, all levels having
the same principal quantum number are degenerate and lie below those of the next
quantum number. Now the effective nuclear charge in the ion increases markedly
because of the net ionic charge and the reduced shidding. [t is not unreasonable to
suppose, then, that the formation of a dipositive ion accomplishes more than the
gradual changes of the entire transition series were able to-that is, lowering the Jd
level so far below the 4s that the repulsion energies are overcome and the total energy
is minimized if the 3d level, rather than the 4s, is occupied. This tendency
hydrogen-like orbitals is dramatic with increasing effective nuclear charge. For example, core electrons are scarcely differentiated energetically according to type of
orbital-they dosely approach the hydrogenic degeneracy.29
Eledron Affinity
Electron affinity is conventionally defined as the energy released when an electron

is added to the V"dlence shell of an atom. Unfortunately, this is in contradiction to
the universal thermodynamic convention that eathalpies of exothermic reactions
shall be assigned negative signs. Since it seems impossible to overthrow the electron
affinity convention at this late date without undue confusion, one can adopt one of
two viewpoints to minimize confusion. One is to let the electron affinities of the most
active nonmetals be positive, even though in thermodynamic calculations the enthalpies are negative:
EA= +328 kJmol- 1
llH = -328 kJ mot-
A slightly different approach is to consider the electron affinities of the atoms to be

the same as the ionization energies of the anions. Now the positive electron affinity
corresponds to an endothermic reaction:
IE= +328kJmol- 1
llH
= -328 kJ mol- 1
This second approach has the added benefit of calling auention to the very close
relationship between electron affinity and ionization potential In fact, when the ionization energies and electron affinities of atoms are plotted, a smooth curve results
and the functiou may be described rather accurately by the quadratic formula: 30
E = aq +
pqz
(2.17)
where is the total energy of the ion (l:1e or l:eA> and q is the ionic charge. See
Fig. 2.13.
It may readily be seen that whereas the acceptance of electrons by active non
metals is initially exothermic, the atoms become
relatively quickly, the
ene.rgy reaches a minimum, and further addition of dectrons is endothermic. In fact,
>t
Forrurlhcrdiscuuionoru.e n:laaiveenclJ)esand reasons. see Kdler, R. N. J. Chm.Uuc. 1962,J9.289;

Hochsarasscr. R. M. lbid. 1965,42. lS4; and Karplus, M.; Poncr. R.N. Atom.r and Molwks; BcrUamin:
New Yorlc, 1970; pp 269-271 .
s"''
a mon accurate expression is a polynomial or the type

+ (lq' + yq> + 6q. The conttants y and 6, however, are
and Eq. 2.17 is a good approximation. Sec IC'l.kowski. R. P.; Marpve.
1. L J. Am. Chml. Soc. 1961, BJ, 3S47.
>O Actually,
The Po l yelectronlc Alo m
41
Fig. 2.13 Ionization

energy-electron affinity
16
curves for oxygen. fluorine.
14
neon, and dllorine.
12
to
1..
0
;;
-1
-2
+I
0
Osiclationmtc
+II
Ill
+IV
for dinegative ions such as 0 2 - and S2 -. the total electron affinity is negative; that is,
their enthalpy of formation is positive. Such ions cannot exist except through stabilization by their environment, either in a crystal lattice or by solvation in solution.
As might be supposed, electron affinity trends in the periodic chan parallel those
of ionization energies (Table 25). Elements with large ioniution energies tend to
have large electron affinities as well. There are a few notable exceptions, however.
Fluorine has a lower electron affinity than chlorine. and this apparent anomaly is
even more pronounced for N/P and 0/S. It is a result of the smaller size of the firstrow elements and consequent greater electron-electron repulsion in them. Although
they initially have greater tendencies to accept electrons (note the slopes of the lines
as they pass through the origin, or neutral a tom, in Fig. 2. 13), they quickly become
as the electron-electron repulsion rapidly dominates (the flat, bottom
portion of the curve). 3 1 Fewer data are available for neutral molecules (Table 2.6).
Free radicals made up of electronegative atoms, such as CN, N0 2 , N0 3 , SF 5, etc.,
have the expected high electron affinities, and we shall see la ter that they are among
the most electronegative of g roups. As a group the metal hexafluorides have the
highest electron affinities with PtF6 having an electron affinity more than double
that of any single a tom (see Problem 2.25).
" For further discussion or dcctron
together with useful Charls and

Wentworth. W. E. J. ChmL EJuc. 1975. 51. 486.
see Chen. E. C. M.:
42
2 The Sh u c tur of Ihe Ato m
7able 2. 5
Ele<Jron afllnillea of the
elements (kJ mol- 1)"
Element
Val.,.
I
2
H
He
3
4
Li
72.775
0
59.63
0
26.7
153.89
7
- 673
-1070"
140.986
- 744
328.0
0
S2.871
0
425
133.6
72.02
-468
-886
200.42
-456'
349.0
0
48.387
0
18.1
7.62
50.6
64.26
0
15.7
63.7
Be
B
N--+N'N'-----+ N 2 N 2 - ----+ N,_
o----+ o o- -o-
9
10
II
12
13
14
IS
F
Ne
Na
Mg
AI
Si
P-pp - pt pt -
16
17
18
19
s - s s- - o s2 -
Ar
K
20
ca
21
22
Sc
Ti
23
24
2S
26
27
28
29
30
31
32
33
Mn
Fe
Co
Ni
Cu
I II.S
118.4
Zn
Ga
Ge
As----+ As'As--+ As -
As'- -
As'-
0
28.9
119.0'
78
- 43s-802"
Element
Value
34
Se--+ Se'-
194.980
- 410"
324.6
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
so
51
52
53
S4
ss
56
51
Se'-- SeBr
Kr
Rb
Sr
y
Zc
Nb
Mo
Tc
Ru
Rh
Pd
Ag
Cd
In
Sn
Sb
Te
I
Xe
Cs
&
La
S8 - 71Ln
llf
72
T:.
13
w
74
15
Re
76
Os
lr
Pt
77
78
79
80
81
82
83
Au
Hg
11
Pb
Bi
84
Po
85
86
AI
Rn
46.887
0
29.6
41.1
86.1
71.9
53
101.3
109.7
53.7
12S.6
0
28.9
107.3'
103.2
190.16
295. 18
0
45.509
0
48
so
0
31.06
78.63
14.47
106.1
151.0
205.3
222.76
0
19.2
35.1
91.2
183.3
270.1
0
Unless otherwise noed. all values are from Hotop. H.; Unc:bc,....., W. C. J. Ploy!f. CMm. Rl!/.
731.
Dolo
b
Pe&nOII, R. G.lnorg. CMm. 1991,30,2856-28.58.
e Miller, T. M.; Miller, A. E. S.; Lineberger, W. C. Ploys. Rev. A 1986,JJ, 3SS8-3S59.
Prol.lems
43
Table 2.6
Eledron ofllnllies of
molecules
Molecvle
bperimentol
(lcJmol-tl"
CH,
752
<:=CH
285
C,H,
C6Hs
C 6H,CH2
CN
OCH,
O-t-C4 H 9
l6S
100
85
365
266
74
232
220
375
42
203
176
ISS
184
Oc.Hs
183
220
N,
NH2
NO
N02
N0 3
o .
o,
OH
0-neo-C,Hu
o.H
104
1..
Maleade
__ _ _ peN_
I
Experimental
1
(lcJ.....r- 1" 1
_ 340
140
SiH,
PH2
ISO
630
770
223
107
...........
<
..
PIF6,
SH
so,
so,
160
20S
SCN
SF, ,
SF,
a.
..
.)
.29()
'tOt I
.1
Br,
TeF,
Tef6
I,
WF
UF1 0
UF6
..;.
_,
,,
2
240
430
320
240
330
325
540
Uas, S. G.; Bartmess. J. E.; l..idlman, J. F.; Holmes, J. L.;

Levin, R. D.; Malian!, W. 0. J . Phys. Chtm. R({. Data 1988,
17, Supplement I. 1-U.
Uncertainly is approllimAtdy ::1:20 eJ:q>t for numbers &iven
to three sCJnificant dia:ils.
Problems
2.1
Calculate the r value in pm at which a radial node willoppear for the 2.s orbital
hydrogen a1om.
2.2
Which quanaum numbers

size of orbitals?
2.3
How many orbil:lls are possible for n
or &he
iruormation about the shape, energy, oriemation. and
4? Which of these may be described as !J<-ra.le?
2.4 How many radial nodes do 3s, 4p, 3d and S/ orbitals exhibit? How many angular nodes'?
2-5 Mnke a photocopy or fig. 2.8. Draw two lines, one along the z axis, and one al a 45
angle away from !he z axis. Along one of the$e lines measure the distance from !he origin
(nuCleus) to each contour line and plot the value of the contour line at that distance
Do this ror all contours on both lines. Compare your drawing with Fig. 2.4,
2.6
Determine the maximum oomber of electrons that can exiSJ in a completely filled n
leveJ. Give four pOSsible quantum numbers for a S/ dectron of the hydrogen atom.
2.7 The signs or the unsquared wave functions are usually shown in plots of the squrcd
functions. Why do you think this prnctice exisls?
2.l! S<lmetimes :!p <>rtliaols are drawn as shown below:
44
2 Th Structure of Jhe AJom
What does this drawing represent? Does it suggest lhat the elearon has finite probability
of being found at the nucleus? We knoW that the probability of finding a 2p electron at
the nudeus is zero. Is this a paradox? Explain.
2.9 Tile angular part of the wave function for the d,, o.-bital is
sin 2 0 sin '24:>. Show
that this expression corresponds to lhe d._ orbital. The d,, is actually a simplified way
of n:presenting the d2,, -x-,, orbital. Show that this corresponds to the angular function,
3cos2 8- I.
2.10 Consider the following possible electron arrangementS for a
r' configuration:
Jlj__ j_j_j_ Jj_j__ j_j_j_

Which of lhese represents the ground state? Which are excited states? Which are impos-
sible states? In wbich configuration would exchange energy be maximized? In which

configuration would coulombic repulsion be maximized?
2.11 The stabilization d a half-filled d shell is even more pronounced than that of lhe p
subshell. Why?
2.12 Discuss the following question: Does an orbital exist if there is not an electron in it?
2.13 The Pauli exdusion principle forbids cenain combinations of m, and m, in determining
the term symbols for the states of the nitrogen atom. Consider an excited nitrogen atom
in which the electronic configuration is ls 22r2p 23p1 What states now are possible?
2.14 Write out electronic configurations for free atoms of the following elements. Decermine
the number of unpaired electrons in the ground state.
Mg
As
Lu
2.15 Determine all of the term symbols for the following free atoms. Choose lhe ground state
term in each case.
Mg
As
lu
2.16 Write out the electronic configurations for the following ions. Determine the number
of unpaired electrons in the ground state.
Gd)+
2.17 Determine the ground state term symbols for each of the ions in Problem 2.16.
2.18 Clearly distinguish the following aspects of the structure of an atom and sketch the appropriate function for Is, 2s, 2p, 3s, and 3p orbitals.
a. radial wave function

b. radial probability function
c. angular wave function

c1. angular probability function
2.19 Using Slater"s rules, calculate
z for the following electrons:
a. a 3p electron in P
b. a 4s electron in Co
c. a 3d elearon in Mn
cl. a valence electron in Mg

Compare the values of
z thus obtained with those of Clementi and Raimondi.
Problems
45
2.20 Which has the higher first ionization energy:
orCs?
For Br7
Sc or Cu?
Cu or Pt?
2.21 Plot the total ionization energies of AI" as a function of n from n

the source of discontinuity in your
I to n
8. Explain
2.22 a. Calculate the third ionization energy of.lithium. [Hint: This requires no approximations or assumptions.]
b. Calculate the first and second ionization energies of lithium using Slater's rules.
c. Calculate the first and second ionization energies of lithium using the rules of C lementi
and Raimondi
2.23 Which is larger:
0 or Br?
Ca1 or znH?
Cs or Fr?
2.24 Which has the highest electron affinity:
U orCs?
OorS?
UorF!
s 01" Se?
Cs or F!
For Cl?
Cl or Br?
2.25 Note that Table 2.6 lists several molecules that have much higher dcctron affinities
than fluorine (328.0 k1 mol-') or chlorine (349.0 kJ
For example, consider PIF6
(m kJ mol- 1). How can a molecule composed or six fluorine atoms and a metal (to be
sure. not a very elearopositive one) ha.e a higher affinity for elcctrons than a flUOI"ine
atom?
2.26 Tile electronegativity of a group is delennined by many oth factors than simply its
electron affinity. Nevertheless, look at the values in Table 2.6 and prcdia what the most
electronegative groups are.
2.27 Which' of the halogens, X 1 would you expect to be most likely to fonn a cation. X 7
Discrete X ions are not known in chemical compounds, but x;. x;. and x; are known.
Why should the latter be more stable than X ?
Chapter
3
Symmetry and
Group Theory
S ymmetry is a rommon phenomenon in the world around us. If NaiUre abhors a

YliCUUJn, it certainly seems to love symmetry! II is difficult to oveteStimate the importance of symmetry in m:1ny aspects of scienc:c, not only chemistry. Just as the
principle known as Occam's l'IIZOr suggests that the simplest explanation for an observation is scientifically the best, so it is true that other things being equal, frequently
one. More important.
the most symmetrical molecular structure is the
the methods of analysis of symmetry allow simplified t reatment ofromplex problems
related to molecular structure.
Symmetry Elements
and Symmetry
Operations 1
Mltthematical symmetry is a lillie more restrictive than is the meaning of the word in
everyday usage. For example. some might say that flowers. diamonds, butterflies, snail
shells, and paisley ties (Fig. 3.1) are all higJIIy symmetrical because of t he harmony
and a ttractiveness of thei r forms and proportions, but the pattern or a paisley tie
is not "lxllancedM; in mathematical language, it lacks symmetry elements. A l!owcr.
crystal. or molecule is said to have symmetry if it has two or more orientations in
space that are indistinguishable, and the criteria for judging t hese are based on symmetry elements and symmetry operations.
A symmetry operation moves a molecule about an axis. a point, or a plane (the
symmetry element) into a position indistinguishable from the original posi tion. If
there is a point in space that remains unchanged under all of the symmetry opera-
46
For lhrcc very sood introdalclory otti<les. - Orchio. M.: .IIITt. H. H. J. Chtm. EJ..r. t 970.
246. 372.
SIO. Amocw lbo bC>I boob arc COfton, F. A. ClwntiNI AppliC'flliotU 11/ C.o"p Tl"""7. Jnl <4.; Wiley:
New Yort. t990. 0ousJas, B. E.; Holllllasworth. C. A. S1fMidry lo B<Huli"ff tJitJ Sp1ro: Ao lllll'llflwc
tlot!; Aaodemic: Otlando, t98S. Ho<Jiuai,
HraiJtlli. M. 5>"""""1 t/ttwglt !11< E;'d of a Chrmlsr,
VCH: New Yort. 1987. Harris. D. c.; llcttolucci. M . D. Sy"""tfr1 and
A.n
Ia
V'JmJiionDI """ Ellctr(Jit/c
Dover. New Vorl<. 1919. Orchin, M.; laiR. H. H. S)lm#Mtry,
Orl>iloh. and Sp.crro: Wiley: New Yort. 1971. Sec abo Wds. A. F. Slrw iWal
ChtMimy.
cd.; Clarendon: Ot<rord. t984;
2.
a..au
Symmetry Elements a nd Symmetry O p aroriotla
47
(c)
4ffr
tb)
10)
(c)
(d)
(a)
(f)
(h)
Fig. 3.1 The sh;tpcs and pauc.rns of some ple<ISing designs found in nature oc constructed as artifuc1s: (a) Ihe flower of the
bloc.k -eyed Susan. Rudbrtkia hlrlo; (b) Jhe Rower. stem. and leaves ol the black-eyed Susan; (c) a red eO. Notophtholmus
lliridrs<Y!ns; (d) a cw diamond; (e) a paisley tie; 10 a snail shell. Crpto nnnorolis; (g) a monarch buuufty. Donou.
p/txippt<: (h) a suspension bridge. Which are truly symmetrical?
41
3 Symmtty and Group Theory
,P
H/ 'a
(b)
(D)
(c)
(d)
Fig. 3.2 Molecules with and withOut mirror planes: (u) dichlorophosphine oxide has a single
mirror plane (the sho:et of the paper) thru reflects the two chlorine :uoms into each other;
(b) water has IWO mirror planes: one which bisects the H- 0- H nngle. the other that ties in
the plane defined by the H-0- H angle; (c) borazine hus four mirror planes: tlvee are of
the vertical lype shown. and the (ooNh is the plane of the ring; (d) melhylsulfinyl chloride has
n11 plane of symmetry. Note thai the lone pair is no1 experimentally observed in the
compound. but has been added to rationalize the molecular structure.
tions, the resultant symmetry is referred to as point symmetry. 2 Molecules may have
symmetry axes, a center of symmetry, and mirror planes as symmetry elements. The
reader will already be familiar with the mirror plane used to help detennine whether
a molecule is optically active.3
The Mirror Plane, u
Most flowers, cut gems, pairs of gloves and shoes, and simple molecules have a plane
of symmetry. A single hand, a quartz crystal, an optically active molecule, and certain
cats at certain times do not possess such a plane. The symmetry element is a mirror
plane, and the symmetry operation is the reflection of the molecule in the mirror
plane. Some examples of molecules with and without mirror planes are shown in
Fig. 3.2.
Center of Symmetry, i A molecule has a center of symmetry if it is possible to move in a straight line from
every atom in it through a single point to an identical atom at the same distance
on the other side of the center (Fig. 3.3). The center of symmetry is also called an
inversion center. We have encountered inversion about a center with regard to a tomic
orbitals, gerade and ungerade, in the previous chapter. Symmetry species of irreducible
representations (see page 59) can also beg or u if a molecule has a center of symmetry.
Of the three most common geometries encountered in inorganic chemistry (Fig. 3.4),
one has a center of symmetry and two do not.
2 Point symmetry or individual molecules Is lo be eontzastcd with the lranJl<lliona/ symmetry or

to be discussed lalt:r in this chapter.
F"sg. 3.3 The center of

symmetry of 1,2-dimethyt1,2-diphenyldiphosphine
disWiide.
> One definition or chirallly is thai the molaculc be nonsuperimposable on its mirror image. An equivalent
crilcrion is that II not possess an improper axis of rotation (plic S2). The eb$encc oC a mirror plane do..
no1 insure oplal activity.bccause a molecule may have no mirror plane. yet may po5SeSS an improper
rot:uional axis. We can. fl9wever, be sure thai the molecule wltlt a mirror plane will be optically inactive.
4
Huhcey, J. E. J . Chem. due. 1986. 6J, 598-600.
Symrftelry Eleme "ta nd Symmetty Operollon
Si
F'fF ' 'F
(a)
Rotational Axis, C,.
Fig. 3.4 Examples of (a)

teuahedrol. (bl trigonal
F F
bipyromidal. and (c)

octahedral geome1ries. Only
(c) hils a centu o(
symmetry. i.
F-P
J'P
F
(b)
49
(c)
If rotation of a molecule by 360"/n result.s in an indistinguishable configuration, the

molecule is said to have ann-fold rotational axis. Consider trans-din itrogen difluoride
(Fig. 3.5). Ir we construct an axis perpendicular to the plane of the paper and midway
between the nitrogen atoms, we can rotate the molecu le by 180" and obtain an identical configuration. Rotation by 180" is thus a symmetry operation.
The axis about which the rotation takes place is the symmetry elemenL I n this
case trans--dinitrogen difluoride is said to have a two-fold rotational axi.s. Note that if
the operation is performed twice, all atoms are back in their initial positioos.5
Now consider cis-dinitrogen difluoride (Fig. 3.6). t possesses no axis perpendicular to the plane or the molecule that allows rotation (other than the trivial 360"
one) and qualifies as a symmetry element. However, it is possible to draw an axis
that lies in the plane of the molecule equidistant between the two nitrogen atoms
and also equidistant between the t wo fluorine atoms. This is also a two-fold axis.
Rotational axes are denoted by the symbol
representing then-fold axis. Thus
cls- and trons-dinitrogen difluo ride each have a C 2 axis.
Note that SiF. (Fig. 3.4a) has. a three-fold axis, CJ. rn fact, it has four of them.
each lying along an Si-F bond. The single t hree-Cold axis in ammonia may be somewhat less obvious (Fig. 3.7a). It lies on an imaginary line running through the center
of the lone pair and equidistant from the three hydrogen atoms. tr aU the bond angles
change, as from 107" in NH J to 102" in NF J does the symmetry change?' Note that
iron pentacarbonyl (Fig. 3.7b) also has a CJ axis. (Are there any other molecules in
c.,
Fig. 3.5 "The two-fold rotational axis in trons-dillitroaen d ifluoride. 'The two-fold axis is
perpendicular to the plane of the paper and de.noced by the symbolt .
Some confusion CUI arise here. We con perform a,mmclly opera lions only if the aloms ;we
able from Cllclt olhcc. Yet ,.e rmaat oltodl invisible Iabeii 10 1hc atoms in onlcr 10
8loms an: bacl< 10 ll1cir inilial positions.
wben
the
No, both NH, and NF, have 1hc same syrnrneuy dcmcrlu. Follow-up qUC$1ion: Wbal ir 1be
bond :qJes be<:orne 11!1'?
A.,.tr: When lhc
become llll". as In DF,, 1ht planar molcculc lw a ltorizonul plane oC
1ymmetry as well as three new C1 ucs lyi in lhat jUne.
SO
3 Symmetry afttl Groul' Theory
...
Fig. 3.6 The lwo-[old ro1atlonal axis in ci.s-dinitrogcn dilluoride.
rtgS.
3.2- 3.7 that have C 3

Note that it also has three C 1 axes, one through
each c:i the carbonyl groups in t he triangular plane that is perpendicular to the C3
axis.
In
tungsten hex.acarbonyl (Fig. 3.7c) has a four-fold axis. In racr., it has
three c.. a.xes: (I) one running from top to bottom, (2) one running from lefi to right,
(3) one running from front to back. (In addition, it has other rotation axes. Can you
find them?8 )
A molecule may posse$5 higher order rotational axes. Consider the eclipsed form
of the molecule ferrocene (Fig. 3.8a), which has a c, axis through the iJ'()n atom and
perpendicular to the cydopentadienyl rings. Now consider the sta@8tred form or
/c.
I
I
I
Ill
o=:c - w- c;;;ro
&
H
I
f..
.N.
I
/
/
,o
Ill
0
(I)
Fig. 3.7 Addi1ional molecules hallina 11told axe.: (aJ ammonin. (b) pcnuocarbcn)'liron.
(cl
' A - . SiF PF,. (CoF.f-. NH,. B,N,H_., Fc(COI.. ond wtCOI. all have om ot more C, aus.
1 Aluwr. wtCOl. has lhrcc
ues, ..,._ C, AJCeS (lllroua/1 IlK ocsallalnl r.c.s).- sia C a.a (lhroush
die OCllhodnl ed&a).
c.
Symme try lle me nu . ,. .. sy,..,.etry Opereti e a a
6'
--- s
---
!'
--Fe:_
Fig. 3.8 Molecules
----- Fe:I
----c.
c,
3'
13'
Cs
c,
(a)
(b)
con-
rot81ion:ll
aJ<CS: (A) eclipsed ferrocene.
,;de liN! lop view: (b)
stuagercd ferrocene. side
and lop iew. Each
molecule has five C: axes.
only one of which is shown.
Upon rolaliOn about the
C: axis. the atoms
interchanae: I .... I'. etc.
40
' --c
3
L_j
51
---
1' 2
Fe
l'
1'
Cerroc;ene (Fig. 3.8b). Does it have a fivefold rotalional axis?' Next ronsider bor.Wne
(Fig. 3.2c). Does it have a C6 axis? 10
Many molecules have more than one C4 axis. For example., staggered ferroccne
has live C: axes, one of which lies in the plane of 1he paper. Edipsed Ji:rrocenc also
has five C, axes, though they are different from 1he ones in the staggered ronformer
(Fig.
In those cases in which more 1han one
axis is present, the one
of highest order is termed 1he principcd axis and is usually the z axis. Planes th:ll
rontain the principal axis are termed vertical planes, u., and a mirror plane perpen
dicular to the principal axis is Qlled a llorirolllal plane, u . For example, borazine
(Fig. 3.2c) has three vertical planes (one is shown) and one horizontal plane (the plane
of the molecule).
Identity, E
Wo:. have seen aboi!C that a C 1 opc:ra1ion (rotation by 360'') rcsuhs in the same molecule thai we started wi1h. h is therefore an identity operation. The ident ity operation
is denoted by . It might appear that such an operation would be unimportant inasmuch as it would accomplish no1hing. Nevertheless, it is included for ma1hematil-ul
rompleteness, and some useful relationships can be const ructed using it For example,
we have seen that two ronsecutive C. operations about the same axis resuh in
identity. We may therefore write: C: X "c: - E. and likewise: c) X c) X c) : e.
These amy also be expressed as
E and
.. E.
C1 ,.
rcrroc.ne bas a five-Cold aais. since: rot:noon ohr.....,. 72'" c:ousa both lhe oop and
bollom rinp to maldllheir lormct posi1ionlc.., lhouah 1hc7 arc 111gcrcd wilh rcspca 10 cac:h ocher.
How.-. edipscd lcrr<><mt also bas a mirror plane pc<pcndk ular 10 ib c, u ls, ohul is abs<:n1 in lhe
lonn. FOf I he rnos1 stable conformalion ol' lcrroccnc and rdatcd compounds, sec Cb:l)lkf u.
10 I f - . No, because rototio of only (/J' pleca A booon AIOfn where lotmcrly there was a niboacn
alom and vice ....._ aon.iroc has a C, OJUs. HC>WCY<t, bctu.cne has a 11\10 axis.
.....,......., Sl2gcrcd
c.
52
3 Sym melry ond Group Theory
Improper Rotation, S,.
A c. axis is often caUcd a

rotational axis and the rotation about it a
"proper" rotation. An improper rotation may be visualized as occurring in two steps:
rotation by 360./n followed by reflection across a plane perpendicular to the rotational axis. Neither the axis of rotation nor the mirror plane need be true symmetry
elements thai can stand alone. For example, we have seen that SiF4 has C3 axes but
no C4 axis. Nevertheless, it has three S 4 axes, one through each pair of opposite faces
of the cube below:
90" rou&ion
Consider the trans configuration of dinitrogen tetrafluoride. If we perform a C 2

operation followed by a q- operation, we will have a successful S 2 operation. Note,
however, that the same result could have been obtained by an inversion operation:
Point Group a and Mole euler Symmetry
53
Fig. 3.9 Coordinate system

and symmetry elements of
the water molecule.
)-,
/ :
I
l
0
/t'\.
____,a;(yu
V1
I
Thus S2 is equivalent to i. Confirm this to your satisfaction with trans-N 2 F2 , which

contains a center of symmetry and thus must have a two-fold improper axis of rotation. Note that the SiF4 molecule, although it possesses true C2 axes. does nor have
a center of symmetry, and thus cannot have an S2 axis. Furthermore, S 1 is equivalent
to a because, as we have seen. C1 E and therefore the second step, reflection. yields
a.II
Point Groups and
Molecular
Symmetry
If we analyze the symmetry elements of a molecule such as water (Fig. 3.9). we find
that it has one C2 axis, two a. planes, and of course E.. This set of four symmetry
operations generated by these elements is said to form a symmelry group, or point
group. In the case of the water molecule, this set of four symmetry elements characterizes the point group c ... The assignment of a point group to a molecule is both
a very simple labeling of a molecule. a shorthand description as it were,2 and a
useful aid for probing the properties of the molecule.
The assignment of molecules to the appropriate point groups can be done on
a purely formal, mathematica l basis. Alternatively, most chemists quickly learn 10
classify molecules into the common point groups by inspection. The following approach is a combination of the two.
These point groups may be defined by the
large number of characteristic symmetry elements, but most readers will recognize them immediately as Platonic solids of high symmetry.
a Icosahedral, 1,.-The icosahedron (Fig. J.lOa), typified by the B12H!i ion
(Fig. 3.10b), has six C 5 axes, ten C 3 axes, fifteen C2 axes, fifteen mirror
I. Groups witlt very high symmetry.
11 1lle chief ruson ror pointing oul 11!= n:lationships is Cor systcmatizJuion: All symmclry
can be included in c.andS, Taken in theonlet in which they were
S1 ; 1- S1 ; E e C,.
Thus when we say lhaJ chiral molecules are ,oo,e without improper axes o( rolluion. the
ol
planes of symmetry and invCf'Sion centers has been included.
11
r.
For eJWnple, the chanist may speak or the

symrmtry or the (Fea.r ion. the
symmetry ol
tbc [PlC14J2 - ion. and the c.. symmetry or the TeO. molecule as alternative ways oC describins the
utralwJrol (Fea.)- ion,the.sq<uvt plontJr [Pea.]- ion, or the structure or the TeCI4 molecule which
ia sometimes called a "bunerflyft molecule.
54
anti Group Theery
i _,
F
'
(II.)
,_
(C)
(b)
(d)
L'"
CN
N
IJI
(h)
(Cl
Fis. 3.1 0 Point sroups and molecules of high symmetry: (al icos:lhetlron.lbl ahe B1:Hli ion, (c) octahedron, (dl sulfur
hexafluoride, (e)
anion. tO cetrahedron,lsl ammonium calion, and (h) letl'lllluoroborllle anion.
planes, a center of symmetry, as well as six S 10 and len

axes collinear
with the
and C) axes.
b. Octahedral, 0 .- lbe octahedron (Fig. 3.10c) is commonly encountered in
both coordination compoonds and higher valence nonmetal compounds
(F'cg. 3. 10<1, e). It has four axes, three C4 axes, six C2 axes.
axes,
three a planes, six a4 planes, a.n d a center of symmetry. In addition, there
are three C 1 and threes.. axes that coincide with the C4 axes.
c. Tetrahedral, T4 . - Tetra hedral carbon is fundnmentallo organic chemistry,
and many simple inorganic molecules and ions have tetrahedral symmetry
as well (Fig. ) . lOg.
A letrahedron (Fig. 3.101) has four C 1 axes, three C 1
axes, six mirror planes, and three
improper rot.ationalaxes.
c,
c,
s.
2. Groaps willt low syi'II/Tietry. There are lhree groups of low symmeuy thai
possess only one or two symmetry dements.
Polnl Orou,a .,... Molo cul er Sym metry
Cl
" ''
II
FCI
'
Br
c,
Cct
Cl
55
Fig. 3.11 Molecules wi1h

low symmeuy: In) phosplloryt bromide chloride
fluoride. C1; (bl ni1rosyt
chloride. C,; (c) 1he anli
conformer ol R.S t.2-
c- c/F
\"H
0
c,
c,
lbl
(c)
dichloro-t .2-dinuorocthanc. c,.
a. C 1.-Molecules of t his symmet ry have only the symmetry element E, equi-
valent to a one-fold rotational axis. Common, simple chiral molecules with

an asymmetric center have only t his symmetry (Fig. l i la).
b. c. - ln addition to the symmet ry element E, which all molecules possess,
these molecules contain a plane of symmetry. Thus although they have
very low symmetry, they are not chiral (Fig. 3.1 I b).
c. C1. - These molecules have only a cen ter of inversion in addition to the identity element. The anti conformations of R.S-1.2-dichloro-1,2-diftuoroethane
(Fig. 3.llc) and R,S-1,2-dimethyl-1,2-diphenyldiphosphine disulfide (Fig.
3.3) have C1 symmetry.
3. Groups with an n-fold rotGiionta/uls, C. . After t.he obvious groups with

high or low symmetries have been eliminated by inspection, the remaining
point groups should be assigned by looking for characteristic symmetry elements, such as an n-fold axis of rotation. c. Molecules containing only one
such axis, like gQuche-H 1 0 1 (Fig. 3.123), tris(2-aminoefhoxo)coball(lll) (Fig.
3.12b), or triphenylphosphine in its most stable conformation (Fig. 3.12c). have
c. symmetry.
in addition to the c. axis. there is a hori:ontal plane pe.,endicular
to that axis. the molecule is said to have c.., symmet ry. An example of this
relatively un important group is traiiS-dichloroethcne (Fig. 3. I 3a). If there are
n mirror planes containing the rotation axis, c. the pla nes are designated
verticcd planes, and the molecule has C.., symmetry. Many simple inorganic
@)J
H.
/c:__
...o H
c,
'
NH.o
/CH:
H1C /
'"6.--NH1
/1--.o
HlC-0 NH,
"
c,
w
(b)
'-CH
CH,/
c,
(C)
Fig. 3.12 Molecules with c. symmary: In)

(b) trist2-aminoclhoxolcob:IIJ<I IIl.
(c) Jriphmylphosphine. The cl :utis in (a) lies in lhe plane oi Jhe pace. Jhe c. axes in (bt
and (c) are pcrpendicutar to 1he paae.
56
!I Symmlry on Gt'oup Theory
'-/
c
II
c
/ 'a
/i,
/'
H H H
NH,
H3N'- ( _.,NH3
Co
HlN
c2,.
c2
c,.
(a)
(b)
(C)
/1'
Cl NHJ
c
(d)
1-CI
H-Ci2!!N
c_.
(c)
{f)
c.,.
Fig. 3.13 Molecules \vith C,,.

and c,.. symmetry: (a) rronsl.2dichloroelhene;
(b) wa1er; (c) ammonia; (d) pentaamminechlorocobalt(lll) calion: (e) iodine monochiOride:
(I) hydrosen cyanide.
molecules such as H 2 0 (Fig. 3.1Jb), NH 3 (Fig. 3.13c), and pentaamminechlorocobalt(III) cation (Fig. 3.13d)13 possess C.., symmetry.
Question: If the planes of the phenyl rings in triphenylphosphine (Fig.
3.12c) were parallel to the three-fold axis
if the intersection of their planes
coincided with that axis). what would the point group of triphenylphosphine
be?'
The point group c.,. is a special case for linear molecules such as ICI
and HCN (Fig. 3.13e, f), because it is possible to rotate the molecule about its
principal axis to any desired degree and to draw an infinite number of vertical
planes.
4.
groups. Molecules possessing nC2 axes perpendicular to the principal axis (C,.) belong to the dihedral groups. If there are no mirror planes.
as in tris(ethylenediamine)cobaii{UI) cation (Fig. 3.14a), the molecule belongs
to the D. group. Addition of a mirror plane perpendicular to the principal
axis results in the D,. groups which include molecules such as phosphorus
[cg r ,,
F,_.... F
f-P
F f
r r
r">( [
Cl
H3N,J ,-NH 3
Co
Cl
Cl
D,
o,.
o4
(Q)
(b)
(c)
F-Bc - f
0=0
H-H
o_.
o_.
o_.
(d)
(c)
(I)
(g)
/(
H 3N Cl
'
NH 3
Fig. 3.14 Molecules wilh D D,,. and
symme1ry: (a) tris<ethylenedinmine)Cobalt(lll) calion. (b) phosphorus

pental!uoride, (c) tetrnchloroplruinale(ll} anion. (d) rruns-tetraamminedichlorocoball(lll) clllion. (e) beryllium dinuoridc.
(f) dioxyaen. (g) dihydrogen.
u The pentumminechlorocoball(lll) calion has

c.. symmetry, that is. I he random orientation or I he hydrogen atoms mulling (rom free ro1a1ion or the ammonia mokcules is oflen ignom! for
simplicity.
o4c..,.
.:.
::.. o4
P lnl Greupa a rul Molecul ar Symmelry
57
c)
I
I
I
I
,,
I
H H....H
c
I
c
D.a,J
H H H
(tl)
/ I'\
I
I
(a)
--@-o-@-'
(c)
(b)
fig. 3.1S Molecules with D..., symmetry: (a) stauered ethane. (bl
tetraearbonyliron))tin. (d) oc1asulfur. (el dibenzenechromium.
nnion. ( cl
pentafluoride (Fig. 3.14b), t he tetrachloroplatinate(II) anion (Fig. 3.14c), the

trans-tetraamminedichlorocobalt(III) cation (Fig. 3. 14d). a nd eclipsed ferrocene (Fig. 3.8a).
Linear molecules with a center of symmetry. such as BeF2 and all of the
Xl molecules (Fig.3. 14e-g), possess a horizontal mirror plane and an infinite
number of C2 axes perpendicular to the principal axis and thus have D><J,
symmetry.
If t he mirror planes contain the principal c. axis and bisect the angle
formed between adjacent C 2 axes, they are termed dihedral plune.f. Molecules
such as the staggered conformer of ferrocene (Fig. 3.8b). the staggered conformer of ethane (Fig. 3. 1Sa), the squarc-antiprismatic octalluorozirconate(IV)
anion (Fig. J.ISb), bis(dimet hyltinbis(lt-tetracarbonyliron)]ti n (Fig. 3.1Sc).
octasulfur (Fig. 3.15d), and the staggered conformer of dibenzenechromium
(Fig. 3.1Se) tha t contain such dihedral planes belong to the D.., groups.
Question: If the triphenylphosphine molecule were planar, what would be
its point group? 1 '
S. A flowcluut for assigning point 11ntf'Mtr1.
The symmetry elements, and

the rules and procedures for their use in determining the symmetry of molecules, can be formalized in a ftow chart such as t hat shown in Fig. 3.16. It
contains all of the poiot groups discussed above (enclosed in square: boxes) as
well as a few others not commonly encountered. In addition, the symmetries
assigned above uby
may be derived in a more systematic way by
the use of this diagram.
IS
D)Jr
sa
3. Symmty and GrOUJt Thoy
Yes
d;
v..
Yes
'F
'F
4C,?
!No
I
v..
o.
0
Yes
'
No
lNo
c,
Mnkcute>of
LowS)'Jllme\1)'
Moluu<s of
HighSym-ry
Fig. 3.16 Flow chan roc assigning the appropriate poim aroup 10 a molc<:ule.
lrreduc.l ble R JM' "'otionl and O...racler Ta ble s
)-
s,
/o;:::
H-+ H-+
lE
o/'\.
H-+ H+I
( ;s}
/o;:::
H-+ H-+
o-
/ '\.
H-+ H-+
lo,.(.t:l
lc,
o-o
/ '\.
-H +-H
(b)
-o
/ '\.
t-H
+-H
59
o-+
/ '\.
H-+ H-+
lct.<rzl
o -+
/ '\.
H-+ H -
-I
+I
(c)
(d)
Fig. 3.17 Effects of symmetry oper.>tions inC,. symmetry; transl:nion along they axis:
(a) identity, E: tbl rot:UiOn aboutJhe c, axis: (c.d) rcAcclion in u ,. planes.
Irreducible
Rapt"esentations
a nd Character
Tables
The symmetry operations that belong to a particular point group constitute a mathe-
matical group, which means that as a collection they exhibit certain interrelationships
consistent with a set o( formal criteria. An important consequence o( these mathematical relationships is that each point group can be decomposed into symmetry
patterns known as irreducible representations which aid in analyzing many molecu.lor
and electronic properties. An appreciation for the origin and signiflCallce o( these
symmetry patte.rns can be obtained from a qualitative development 16
Until now we have considered symmetry operations only insofar as they affect
atoms occupying points in molecules, but it is possible to use other references as well.
For example, we might consider how a dynamic propeny of a molecu.le, such as
translation along an axis. is transformed by the symmetry operations of the point
group to which the molecule belongs. Recall the symmetry elements and coordinate
system given previously for the water molecule, which belongs to the c,. point group
(Fig. 3.9). The coordinates are assigned according to the convention-that the highest
fold axis of rotation-C2 in this case- is aligned with the z axis, and the x axis is
perpendicular to the plane of the molecule. Now let translation of the molecule in
the + y direction be represented by unit vectors on the atoms, and imagine how they
will change when undergoing the Cz. symmetry operations (Fig. 3.11). At the end of
each symmetry operation. the vectors will point in either the + y or the - y direction,
that is, they will show either symmetric or antisymmetric behavior with respect to
the operation. If we represent the former with +I and the latter with -I, we can
each oper.uion with one of these labels. Identity (E) does not alter the
position of the arrows ( + 1). Rotation about the C1 axis causes the + y vectors to
change to - y ( - 1). Reflection in the a.(x=l plane causes + y to change to - y ( - I),
but rellection in the plane of the molecule.
results in the vectors remaining
unchanged ( + 1). The set of four labels (+I, -I, -I, +I) generated in this simple
analysis constitutes one irreducible representation within the C 2 pOint group. II is
irreducible in the sense that it cannot be decomposed into a simpler or more fundamental form. Not only does it describe the effects of C1 operations on y translation
but on other "y-vector functions" as wen, such as the p7 orbital. Thus y is said to
serve as a bu.risfunclioll for this irreducible represenlation within the C 2 point group.
16
For mor 1horough and maJhematK:.d developments in terms or group theory, seethe boob listed in
F001no1e t.
60
3 Symmetty anti G r oup Theory
;-,
/ 'H
iE
!c:
/o,
ll
Az
ll
/'
H
/o,
/o,
ll
ll
lo;Cyl)
o.(xtl
/o,
/o,
/o,
+I
+I
(o)
(b)
(c)
(d)
Fig. 3.18 Ell'ects of symmetry operations in Cz. symmetry; roJalion about Jhe l axis:
(a) identity. E; lb) rotation about the C1 ax.is. (c, d) reflection in u. planes.
Translations (and p orbitals) along the x and z axes in the water molecule conform to different symmetry patterns than the one just developed for they axis. When
the , C2 , a.(xz). and u.(yz) operations are applied, in that order, to a unit vector
pointing in the + x direction. the labels +I, - I, + I, and - 1 are generated. A vector
pointing in the +z direction wiD be unchanged by any of the symmetry operations
aod thus will be described by the set: + I, + l, + I, + I.
The principles of group theory dictate that the total number or irreducible representations belonging to a point group will be the same as the number or types or
or symmetry operations characterizing the group. Hence we expect four irreducible representations for the Cz. point group. We can generate the fourth one by
considering rotation of the water molecule about the z a.xis. To see this, imagine an
arrow curved dock wise about the z axis (when viewed down this axis; see Fig.
Like the linear translations, this motion will be symmetric with respect to any operation that causes no change in direct.i on and will be antisymmetric for a ny operation
that leads to reversal Both E and C1 leave the d irection unchanged (+ I), but reflection in either mirror plane causes a reversal ( - I). The result is +I, +I, - I , and
- I as the founh symmetry pattern for the C1 group.
Many or the symmetry propenies of I point group, including its characteristic
operations and irreducible representations, are conveniently d isplayed in an array
known as a character table. The character table for C1 is 11
Cz.
A,
Az
B,
Bz
Cz
a.(xz)
a'.(yz)
I
I
- I
-I
I
- I
I
- 1
- I
- 1
I
xz, yz, zl
R.
.x, Ry
y,R.
xy
xz
yz
The column headings are the classes of symmetry operations for the group, and
each row depicts one irreducible representation. The + I and - I numbers, which
., Characaer lables Cor other point povps can be fouod In Appendix 0.
lnedvcible Repre1entations and Charader Tables
61
correspOnd to symmetric and antisymmetric behavior, as we have seen, are caUed

characters.
In the columns on the right are some of the basis functions which have the
symmetry properties of a given irreducible representation. R., R1 , and R, stand for
rotations around the specified axes. The binary products on the far right indicate,
for example, how the d atomic orbitals will behave ("transform") under the operations
or the group.
The symbols in the column on the far left of the character table (Mulliken labels)
are part of the language of symmetry. Each one specifies, in shorthand form, several
features of the representation to which it is auached. One such feature is the dimension, which is related to the mathematical origin of the characters. Strictly speaking.
each character is derived from a matrix representing a symmetry operation, and is
in fact equal to the sum of the diagonal elements of the matrix. For the C2v group.
all or these matrices are of the simplest possible form: They consist of a single element
(the character) and are thus one-dimensional. However, for groups with rotational
axes of order three or higher, two- and three-dimensional matrices occur, leading tO
characters with values as high as 2 and 3, respectively. (This will be illustrated shortly
point group.) One-dimensional representations, such as those in the c2v
for the
group, are labeled A if symmetric or B if antisymmetric with respect to the highest
order rOI:ational axis. If two or more representations in a group fit the A or B classification, a subscript is added to indicate symmetric (I) or antisymmetric (2) behavior
with respect to a second symmetry element. This second element will be a C2 axis
perpendicular to the principal axis or, in the absence of such an axis, a vertical mirror
plane. Two-dimensional representations are denoted by E (not to be confused with
the identity operation E), and three-dimensional cases by T. As we have seen before,
the labels g and " may be applied if there is a center of inversion. The superscripts '
and " may be used to signify symmetric and antisymmetric behavior with respect to
a horizontal plane.
.
The tetrachloroplatinate(ll) anion. PtCI!-, was given earlier (Fig. 3.14c) as an
example of a molecule belonging to the D41, pOint group. The character table for this
group is
v."
D""
2C
:A,,
Az,
I
I
I
I
-I
- I
B,,
i B21
fE,
f
1
2
I
Az.
[ B'"
Bz.
E.
'
b _
l
1
I
2
0
I
1
-I
-I
Cz
2C2
2Cl
- I
- I
I
-I
0
I
-f
2S.
I
I
-I
I
I
-2
1
l
1
I
-2
0
l
-1
-1
I
-I
-I
f
2
-1
-1
0
-I
2u.
u.
2u4
x2 + yz, 1 1
l
I
I
-I
I
-2
-I
-I
0
-I
-1
- I_
-I
R,
-I
-1
-1
-I
I
-I
--1
-I
- I
-2
-I
2
(R., R 1)
xZ-yZ
xy
(xz, yz)
z
(x,y)
Note that two of the irreducible representations in this group are two-dimensional,
labeled E, and E. Each bas a paU- of basis functions listed for it. To see how x and
y translation serve as a basis for the E. representation. refer to Fig. 3.19 which shows
, the PtOi- ion labeled with a coordinate system assigned according to the usual
conventions. The z axis coincides with the C4 rotational axis, and the x and y axes
J-
Fig. 3.19 The Ftdl ion (D..l with x und y

translation veaot'S.
y -- -
c;.a.
are aligned along the Pt-CI bonds, as shown. The C1 and C'i axes are secondary
axes perpendicular to C4 The C1 axes are chosen so as to include as many atoms
as pos51ble, and thus they lie along t.he x and y coordinates. The Ci axes lie midway between the x andy axes. The u. and u 4 planes include the C1 and Ci axes,
respectively.
Translation of the PtCI!- ion in the x and y directions can be represented by
the two vectors shown on the platinum atom (Fig.
In cont rast to all or the
cases we have so far considered, certain operations or the D... group lead to new
orientations for bot h vectors that do not bear a simple + I or - I relat ionship to
the original positions. For example, under a clockwise C 4 operation, the x vector
is rotated to the + y direction, and the y vector is rotated to a -x position. The
character for this operation is zero. (This arises because the diagonal elements of the
matrix for this operation are aU zero; other elemalls in the matrix are nonzero but
do not contribute to the character.) The and a. operations lead to a similar mixing
of the x and y functions and also have characters of zero. Because of this mixing.
the x and y functions are inseparable within the D... symmetry group and arc said
to transfonn as a doubly ckgenerate or two-dimensional representation.
The remaining charac.ters of the E,. representation can be generated by considering the combined effect of each operation on the ,'( and y vectors. When the
identity operation is applied, both vectors remain unchanged; hence the character
for the operation is two times + I or + 2. Similarly, the a. operation (rcOection in
the plane of the molecule) leaves the vectors unmoved and yields a ch:uacter of + 2.
Under the C 2 operation (around the z axis), the x vector is brought to a -x position
and the y vector to a - y position, giving a character of 2( -2. Inversion
through the center of symmetry leads to the same result. For a Ci operation around
they axis, they vector is unaltered ( + 1), while the x vector is rotated to the opposite
direction (- 1), yielding a total character or zero. The outcome is identical for reflection through t he mirror plane that includes the y axis (a a.
s.
Re ducible
Representations
In awlying the methods of group theory 10 problems related to molecular s.trua.ure

or dynamics, the procedure that is followed usually involves deriving a reducibk
representation for the phenomenon of interest, such as molecular vibracion, and then
decomposing it into its irreducible components. (A reducible representation will
always be a swn of irreducible ones.) Although the decomposition can sometimes
be accomplished by inspectioo, for t he more general case. the following reduction
Uses of Point Group Symmelry
63
formula can be used:

(3.1)
h"
fn this expression, N is the number of times a particular in-educible representation

appears in the representation being reduced, h is the total number of operations in
the group, X: is the character for a particular class of operation, x, in the reducible
representation, X: is the character of x in the irreducible representation. n is the
number of operations in the class, and the summation is taken over all classes. The
derivation of reducible representations will be covered in the next section. For now,
we can illustrate use of the reduction formula by applying it to the following reducible
representation, r, for the motional degrees of freedom (translation, rotation, and
vibration) in the water molecule:
E.
r,:
o,(xz)
o.(yz)
To decompose this representation, Eq. 3.1 must be applied for each of the four irreducible representations in the C1 point group:
A 1:
=!!)((9)(1)(1) + (-1)(1)(1) + (1)(1)(1) + (3)(1)(1)] = 3
A1 :
= W((9J(I)(l) + (-1)(1)(1) +(IX -1)(1) + (3)( -I)( I)]= I
8 1:
N = (!)((9)(1)(1) + (-I)( - I)( I)+ (1)(1)(1) + (3)(- 1)(1)] = 2
B 2:
N = Hl[(9)(1)(1) + (-l)( -I)( I)+ (I)(- 1)(1) + (3)[1)(1)] = 3
Thus the reducible representation is resolved into three A 1, one A 2 , two B 1, and
three B 2 species. lt can easily be confirmed that the characters for this combination
Sum !O give the characters Of r,.
Uses of Point
Group Symmetry
Optical Activity
The reader will already have encountered chirality extensively in organic chemistry
based upon asymmetric carbon atoms. Although the usual definition of chirality in
organic texts is based upon a nonsuperimposable mirror imagc 18 and thus allows
chirality in species such as helicene and spiro compounds, few introductory organic
texts discuss chirality other than that based on asymmetric carbon atoms.' 9 Inorganic
molecules may be optically active based on asymmetric nitrogen, phosphorus, or
sulfur atoms,10 but by far !he largest number of chiral inorgan ic compounds do not
have a single asymmetric atom at all, but are chiral because of the overall molecular
symmetry, specifically the absence of an improper axis of rotation. Most of these are
11 As we have seen, the (onnal definition Of Optical ac1ivi1y is b-.JScd UpOn tiM: a"'"'n<:e olan improper WI is
of rotution. The two definilions :are equivalent.
For di$cussions ol cflinl organic molecules thnl do nnt contain asymmetric corbon atoms. sco: Wodc.
L. C . Jr. OrgDnlc C'-dstry; Prentice-Hall: Enslcwood Cliffs. NJ. 1987; pP JS4- l.56.
K. Tnpics
Cwr. Clum. t984, IZJ, 27. Laamoven, W.
Prinsen. W. J. C lb/J. 1984, 11J. 6J. Meurer, K. P VlSlle,
F. Ibid. 1985. 117. I.
10 The"" are discuS>cd in Chapter 6.
64
3 Symmetry and Group Theory
Table 3.1
Point gr....,s of chiral cmd
ac:fWal molecules
1
Cltlral
Adllral (lclenllfylng
C, (asymmetric)
C, (plane or symmetry)
D. (dissyiiUIIetric)
o.. (planeofsymmetry)
c. (dissymmetric)
c, (center
element)
- "-
D.4 (plane of symmetry)
s. (improper axis)
T 4 (plane of synvnetry)
o. (center and plane of S}'lll!lletry)
1. (ceotee and plane of symmetry)
c.. (plane ofsymmetry)
six-coordinate complexes with D3 or closely rdated symmetry. They will be discussed
at greater length in Chapter 12. Since chiral molecules often possess some elements
of symmetry (e.g.. both Cz and C 3 are found in the D3 point group). it is not appropriate to refer to them as asymmetric (without symmetry). These molecules have come
to be known as dissymmetric and this is, in fact, the term now used for aU chirdl
molecules. The absence of an improper axis of rotation defines a molecule as dissymmetric (see Footnote 3). Common point groups are categorized as chiral or achiral
in Table 3.1.
Dipole Moments
Tahle3.2
Paint groups f wt.ich
dipole momenh are
symmetry alowed ar
symmetry forbiclclan
A molecule will have a dipole moment if the summation of all of the individual bond
moment vectors is nonzero. The presence of a center of symmetry, I, requires that
the dipole moment be zero, since any charge on one side of the molecule is canceled
by an equal charge on the other side of the molecule. Thus (CoF 6]l- (Fig. 3.4c),
trans-N 1 F 1 (Fig. 3.S), and the staggered conformer of ferrocene (Fig. 3.8b) do not
have dipole moments.. If two or more c. axes are present (n > 1). a dipole cannot
exist since the dipole vector cannot lie along more than one axis at a time. Thus
SiF4 (Fig. 3.4a), PFs (Fig. 3.4b), eclipsed ferrocene (Fig. 3.8a). and all D. molecules
(cf. Fig. 3.14) do not have dipole moments. The presence of a horizontal mirror plane
prevents the possibility of there being a dipOle moment, but one or more vertical
mirror planes do not. The dipole moment vector must obviously lie in such planes,
and there may be a c. axis in the plane along which the dipole lies. Examples of
such molecules are cis-N 1 F 1 (Fig. 3.6) and O=N-CI (Fig. J.llb). Common point
groups are listed as "symmelry allowed" or "symmetry forbiddenM with respect to
possible dipole moments in Table 3.2. In addition, it is always possible that certain
, . 7...
- .
Symmetry allowed
Uses o f Point Group Symmetry
S""l>l< cell
'o
IR 6Jht source
Rcl"<:r=:c
ed
'o
An infnted expcrimenl
Jncidc:n tiglll
Vi.sible &aser
Is
65
IR
dclcctor
"'
S4lmple
Seoue...S
tigi'C
pllo<oo
court.tet
A Romlltl upcrimooc
Fig. 3.20 Schematic repr=ntation of infrared and Raman experiments. In infrared

spectroscopy the excitations are detected by absorption of charactef'istie frequencies. In Raman
spectroscopy the excitations are detected by characte<-istic shifts in frequenc.ies of the
scanercd light. [From Harris, D. C; Benolucci, M. D. Symmetry ond Sfl<lctroscopy; Dover:
New York, 1989. Reproduced with permission.]
heteronuclear bond moments might be zero. or two different bonds might have identical moments that cancel. Indeed, some molecules have very small but finite dipole
moments: S=C- Te (O.S7 x
C m; 0.17 D), cis-FN=NF (O.S3 x 10- 3 C m;
0.16 D), NO (0.50 x 10- 3 C m; 0.15 D), SbH 3 (0.40 x 10- 3 C m; 0.12 D). CO
(0.37 X w-lo m; 0.11 D), FCI03 (0.077 X 10-JO m; 0.023 D).
Infrared and Ra man

SIDectroscoiDV
In infrared spectroscopy photons having energies corresponding to the excitation of

certain molecular vibrations are absorbed and the transmittance of the infrared light
at those frequencies is reduced (Fig. 3.20). In Raman spectroscopy, allowed molecula r
excitations result in differences in the frequency of scattered light. Thai is, incident
light, which may be of any wavelength (usually visible), undergoes scauering. Most
of the scattered light has the same frequency as that impinging upon the sample. but
the frequency of a small fraction is shifted by amounts corresponding to the energy
differences of the vibrational states (Fig. 3.20).
The number of vibrational modes of a molecule composed of N atoms is JN- 6

(or 3N- 5 if linear). 21 We may find which of these are infrared and Raman active
by the application of a few simple symmetry arguments. First, infrared energy is
absorbed for certain changes in the vibrational energy levels of a molecule. For a
vibration to be infrared active. there must be a change in the dipu/e moment vector
" The molecule wiU have a total of 3N dqrces of freedom. or wflich three will be ;usoc:ialed wilh trans-
lation and another lhree (two if linear) with rolalion.
66
, - Sy"""'olry en4
Th oory
;-,
T
/o,
/o,
E.
.lo
""/ v,'H\,
'!-'
1. C
c;. lo.
T
/o,
/o,
"-!'
+I
"
"
(0)
(b)
!e.
1c o.<;)
1
,H,
/a
'Y
+I
lo
0\,
,..,/ 'H'-
-I
+I
B:
(c)
Fig. 3..21 Normal modes of vibr.uion of she w.uer molecule: (a) symmelrical s1re1ching
mode. A,; Jb) betiding mode. A1; (c) anlisymmetrical SlteiChina mode. B:. and 1heir
aransrormarions under cl. symmelry opcraaions.
associated with the vibration. Consider the very simplest molecules possible. In X 2
molea.oles there will be only one stretching vibnuion, there will be no change in dipole
moment (bec:luse there is no dipole moment either before or during vibr:ltion as long
as the two X atoms are identical), and so th::ll vibration will not be infrared active.
The molerules Hz. F2 , Oz, lll1d N 2 show no IR absorptions. However, carbon monoxide, isoelectronic with dinitrogen, has a saml l dipole moment. :uxl the molcwlar
vibration is infrared uctive because the dipOle moment ch11ngcs as the bond length
changes. The absorpcion frequency is 2143 em- a, an important value for coordination chemistry.n The poinc is that the electromagnetic infrared wave can interact
with the electric dipole moment.; in essence, the infrared wave's electric field can "grab"
the vibrating electric dipole moment resulting in a molecular vibration of the same
frequency but increased amplitude.
Consider next the water molecule. As we have seen, it has a dipole moment. so
we expect at least one t R-active mode. We have also seen that it has C z. symmetry,
and we may use this fact to help sort out che vibrational modes. Eocla normal mode
of
will form a basis for 011 irreducible represeutatiou of rile point uroup of the
molecule.l 3 A vibrmiotl will be infrared actiw !firs uormol mode bt!lougs to u11e if
irreducible representarions corresponding to t.hc x, y and z
The C 2 character
table lisiS four irreducible representations: A,. A1 , 8 1, and 8 2 tr we examine the
three normal vibrational modes for H 1 0, we see that bot h the symmetrical stretch
and the bending mode a re symmetrica l not only with respect to the C 2 axis, but also
wit h respect to the mirror planes (Fig. 3.21). They therefore have A 1 symmetry and
since z transforms as A,. they are IR active. The third mode is not symmetrica l wit h
respect to the C 2 axis, nor is it symmetrical with respect to the cr,.(xz) plane, so it
has 8 1 symmetry. Because y transforms as 8 1 , this mode is also IR act.ive. The three
vibrations absorb at 36S2 em - , I S4S em 1, and 37S6 em - , respectively.
11 See
II and IS.
u For a mo<c
discussion ol
Bertolllcti, M.D. S)'IMIC(ty Olt4
P:""'' abco<y
and vibralian:ll apccttosc:op7, ..,.
Dcnoa: New Yort, 1989, Cbaprer 1
Harris. D. C;
Usn of Point wovp Symmetry
67
Toble3.3
O.nYOiion of reducible
ropreMftlolion f<K degrees
of freedom in the molecule
c.
Uruhifted atoms
Contributioo per atom
3
3
I
- I
r,.,
- I
O',(n)
cr,hz)
For a vibration to be Raman active, there must be a change in the polarizobility
censor. We need not go into the detai.ls of this here, u but merely note that the components of the pelarizability tensor tr.tnsform as the quadratic functions
Table 3.4
Atomic cofllributions, by
symmlllry o,.rotion, lo Jh
rHUcible repr...,llllien for
lhe 3H deer- of lroeclom
for o "'alecvle
Operatiorl
c.
c,
c.
c.
"
ea..triburioa
..... __.
3
- 1
0
I
2
I
s,
s.
s.
C, l
s. - -
y, and
z. Therefore, in the char:ader tables we are looking for x1, y 1, z2, xy, xz, yz, or their
combinations such as x 1 - y. Because the irreducible representation fo r x 1 is A 1
and that for yz is 8 2, all three vibrations of the water molecule are Raman active
as well
-3
-2
- 1
0
The foregoing analysis for water relied on our ability to describe its fundamental
vibrational motions as a first step. Although this is a relatively simple rask for an AB1
molecule, it becomes formidable for complex structures. An al ternative procedure can
be used which requires no knowledge of the forms of the vibratioau. It begins with
the derivation of a reducible representation for all 3N degrees of freedom for the
molecule. This can be accomplished by representing the degrees of freedom for each
atom as a set of Cartesian displacement vectors chosen so that the : vectors are
parallel to the molecule's highest fold rotational axis (F ig. 3.22). The characters of
the reducible representation can then be determined by considering the combined
effect of each symmetry operation on the atomic vectors. A simplification is possible
here because only those atoms that are not shifted by an opera.t ion will contribute
to the character for that operation. For water, this includes all three atoms for both
the and a-.tyd operations. but only oxygen rur the other two (Table 3.31. The contribution of each unshifted atom to the total character will be I he sum of the effects
of the operation on the atom's displacement vectors. For the
operation.. a
vector will either remain stationary ( + I) or be shifted to minus itself (-I). Thus we
obtain + 3 for the identity operation because all three vectors are unaffected. In the
case of C2 , the vector on the oxygen :110m remoins stationary while the x and y
vecto rs are moved to - and - )', respectively, yielding an overall value of - I.
Because these contributions are independent of molecular symmetry, they can be
conveniently tabulated for common operations (Table 3.4). A simple multiplication
I +2cos
360
n
)-.
Fig. 3 .22 Cartesian

displactment vectors ror
the water molecule.
Ehswor1h. E. A. V.: Rankin D. W. H.: tndock. S. SlrWtr,.ol M"lw' S
68
3 Symmetry and Group Theory
Table 3.5
O..ivation of
r ... ,.,. Bel,
Unshifted atoms
Contributioos
per atom
r,.,
2C,
3C.
2
a
4
25,
-I
-2
12
-2
-2
3a.
of the number of unshiftcd atoms by the contribution for each operation gives the
reducible representation (r,..) for water shown in Table 3.3.
We determined earlier (page 63) that the irreducible components of this representation are three A 1 , one A2 , two B 1 , and three B1 species. To obtain from this
total set the representations for vibration only, it is necessary to subtract the representations for the other two forms of motion: rotation and translation. We can identify them by referring to the C z character table. The three translational modes will
belong to the same representations as the x, y, and z basis functions, and the rotaR,, and R:. Subtraction gives
tional modes will transform as
r,.. = 3A L + Az + 28, + 38:

- (r,,.., = A ,
+ B, + B2 ]
-(r,., =
A2 + B1 + B 2 ]
r.lb = 2A, + B:
This is, of course, the same result as obtai.ned above by analyzing the symmetries of
the vibrational modes.
As a second example of the use of character tables in the analysis of IR and
Raman spectra, we turn to BCI, with D 3 symmetry. Because it has four atoms, we
expect six vibrational modes, three of which will be stretching modes (because there
are three bonds) and three of which will be bending modes. Table J.S shows the
derivation of r 101 for the molecule's twelve degrees of freedom. Application of the
reduction equation and subtraction of the translational and rotational representations gives
r,., =
A'1 + A% + JE' + 2A'; + E"

E + A';
)
A% +
+ E"]
r.,.. = A'1 + 2E + A%
-[r,..., =
- (r,., =
We see that the six fundamental vibrations of BCI 3 transform as

A';, and 2'.
Each E' representation describes two vibrational modes of equal energy. Thus the 2E'
notation refers to four different vibrations, two of one energy and two of another.
The A; mode is Raman active, the A% is IR active, and the ' modes are both Raman
and IR active.
In thinking about the actual vibrations associated with these modes, we expect
the A'1 mode to be the symmetrical stretch because it remains unchanged under all of
the symmetry operations (Fig. 3.23a). Another motion is a symmetrical out-of-plane
bending deformation with the boron atom moving in one direction while the three
chlorine atoms move in unison in the opposite direction (Fig. 3.23b). The four remaining vibrations (two stretching and two bending} are not as easily categorized
because they are distributed among two doubly degenerate modes, both of which
Uses of Point Group Srmmefry
oact3 47t em-
1080 995 cm- 1

11 0Ct 3 9S6 cm- 1
3
11 B0 47t em
1
108CJ) 480 em I
11
80, 460 cm'" 1
A'I
A!'
(a)
(b)
I c)
.,
"z
.,
69
10 BCJ 244rn.- 1
11 BCt 3 243 cm- 1
3
"4
F:
Fig. 3.23 Nonnal modes of vibr.Uion of Ihe BC13 molecule: (a) symmecrical
mode, Aj ; (b) out-of-plane bent.ling mode, A!; (c) unsymmeuical stretching mode, '; and
(d) in-plane bending mode. E'. [Modified from Harris. D. C .; Benotucci. M. D.
ond
Dover: New YOI'k. 1989. Reproduced with permission.!
belong to'. Figure 3.2Jc and d show one component of each of these modes; in each
case, the two components give rise to a single frequency of vibration. Both c and d
are restricted to the xy plane and can thus have only x and y components, and so
both modes can be no more than doubly degenerate. Both are symmetric with regard
to the horizontal mirror plane, so they transform as E.', not E'.
Another useful "trick" in interpreting spectra is the fact that the characteristic
frequency of a vibrational mode will depend upon the masses or the atoms moving in
chat mode. Isotopic substitution can thus be used to assign some of the frequencies. 25
Note that in a pcrfecl.ly symmetrical stretch, the boron atom moves not at all. and so
substitution of 10 8 for the more abundant 11 B will leave the absorption unchanged
at 471 cm- 1 (see Fig. J.2Ja). In contrast, the boron atom moves considerably in b
and c and substitution of the lighter ' 0 B results in shifts of these absorptions to higher
frequencies. Vibration d is interest.ing-to a first approximation the boron atom
scarcely moves. But move it does, tending to follow, feebly to be sure. the single Cl
atom in opposition to the pair of Cl atoms. The absorption frequency hardly changes,
from 243 em 1 to 244 em- 1, upon isotopic substitution.
We have seen that not all molecules are like water in having all vibrationlll
modes both IR and Raman active. In fact, there is ao extremely useful exclusion rule
for molecules with a center of symmetry, i : If a molecule has a center of symmetry. I R
and Raman active vibrational modes are mutually exclusive; if a vibration is I R active,
i1 cannot be Raman active, and vice versa.26
An example to which this rule applies is XeF4 In fact, it nicely illustrates the
usefulness of IR and Raman spectroscopy in the assignment of structures. For XeF 4
we expect nine vibrational modes, four stretching and five bending. These are illustrated in Fig. 3.24. Note that like BCI,, XeF4 has two modes that are doubly degenerate (E.). The importance of the vibrational spectroscopy of XeF4 comes from the
u Other dues may be used ol course. FOC' Cllllmp!e, it is usually observed that asymmetric stretches occur
at higher frequencies than symmetric stretches, lhoul!h there are excepeions.
14
Note that white it is impouiblc Cor a molecule wilh a center or symmetry to have a
that is
both IR and Raman active. it Is possible for ir co have a vibration lhru is Mithu. See Keiter, R. L
J . Chmt. due. 1983, 60, 62S.
70
3 Symmetry and Gl'ovp Theory
I
I
I
I
-- -
+x---I+
I
I
- -l91an-'
I
I
,;g. 3.24 Normal modes

of vibration of the XcF4
Note that both
E. modes arc doubly
degenerate. [Modified from
Harris. D. C; Bertoluoci.
M. D. Symmetry and
Spcroscopy. Dover: New

York, t989. Used with
pennission.)
1
-
I
-- -
123cm" 1
fact that when the first compounds of noble gases were synthesized there was considerable uncertainty about their structures. For XeF4 some chemists of a theoretical
bent opted for a tetrahedral structure, while most inorganic chemists interested in
the problem leaned tOw.trds a square planar structure. The matter was resolved by
Claassen. Chernick, and Maim in a paper entitled
Spectra and Structure
of Xenon Tetrafluoride." 27 The opening sentences of their abstract reud as follows:
"The infrared spectrumofXeF. vapor has slrong blinds at 123.291. and SUcm .
Tile Ramnn spectrum of the solid has very intense peaks at 502 and 543 em - and
weaker ones at 235 and 442 em-. These data show that the molecule is planur and
of symmetry D41, ...
Claassen and co-workers made the assignments shown in Fig. 3.24. The weak absorption at 442 em - 1, which does not appear in Fig. 3.24, was ruled out as a fundamental and assigned as an overtone of B2 A glance at the character table foro._
(for square planar XeFJ shows that the B 2 mode is neither IR nor Raman active.
Its frequency was obtained from the overtone (442 em -). which is Raman active. 28
T he important thing to note is that if XeF4 is square planar, it will have a center
Cla:uscn, H.
Che.-nidt. C. L.; Maim. J. Q . J . Am. CNm. Soc. t963. 8J, 1927-1928.
"'The repreocnh>lion ror the over1one may be obhtined by ._ina the irreducible repre>ctUllllon f<>r B,.,
18:. x 8,. A1. ). The r..ull. A, .. oromform. as a binory product and lherefOfe is !Wrton llc.livc. FU<
a discussion of dire<:! producU of Rp>enl41ions as applied 10 oertones. S foolnok 24.
u...
of Poi11t Group Symmetry
71
of symmetry, I, and none of the IR and Raman bands can be coincidental: if it

were tetrahedral, there should be IR and Raman bands at the same frequencies. T he
presence of six fundamental bands, three in the infrared and three in the Ramnn,
none coincidental, is very strong evidence of the square planar structure of XeF4
Bonding
Covalent bonds can be described with a variety of models, virtually all or which
involve symmetry considerations. As a means of illustrating the role of symmetry in
bonding theory and laying some foundation for discussions to follow, this section will
show t he application of symmetry principles in t he construction of hybrid orbitals.
Since you will have encountered hybridization before now, but perhaps not in a symmetry context, this provides a facile introduction to the application or symmet ry.
You should remember that the basic procedure outlined here (combining appropriate
atomic orbitals to make new orbitals) is applicable also to the derivation of molecular
orbitals and ligand group orbitals, both of which will be encountered in subsequent
chapters.
The atomic orbitals suitable for combination into hybrid orbitals in a given molecule or ion will be those that meet certain symmetry criteria. The relevant symmetry
properties or orbitals can be elUracted from character tables by simple inspection.
We have already pointed out (page 60) that the p6 orbital transforms in a particular
point group in the same manner as an :r vector. In other words, a P,, orbital can
serve as a basis function for any irreducible repteSCntation that has
listed among
its basis functions in a character !able. Likewise, the p, and p, orbitals transform as
y and z vectors. The d orbitals-d.,, d., d,., d,.._,,, and d,,- uansform as the binary
products xy, xz, y:, x'- yl, 01nd z:1 , respectively. Recall that degenerate groups or
vectors. orbitills, etc.. are denoted in character tables by inclusion within pareotht$C$.
An s orbital, bec11use it is spherical, will always be symmetric (i.e., it will remain
unchanged) with respect to all operations of a pOint group. Thus it will always belong
to a representation for which nil characters are equal to I (a
representation), although this is not explicitly indicated in character tables. The totally
symmetric representation for a paint group always appears first in its character table
and has an A designation (A 1, A,, A 11,
When these or any other Mulliken symbols are used to label orbitals or other one-electron functions, the convention is to
use the lower case: a,. a,, etc.
To sec how the s, p. and d atomic orbitals on a central atom are affected by t he
symmetry or the molecule to which they belong, consider the oc.tahedral (0,}, square
pyr.tmidal (C... and seesaw (C2.) species shown in Fig. 3.2S. For the AB6 case, we
find from the character table for the
point group (Appendix D) that the p., p,.
and p, o rbitals belong to the 11 representation. Since they transform together, they
represent a t riply degenerate set. The live d orbitals, on the other hand, fo rm t wo sets
of degenerate orbilals. T he d. - r and d,. orbitals belong to the doubly degenerate
e, representation and the d.,. d.,, and d,, orbitals transform together as a t riply
degenerate 111 set. The s
as always, belongs 10 the totally symmetric representation, a 11.
If we imagine removing one of t he B atoms from A8 6 , we are
with square
pyramidal AB, (Fig. 3.25b). By referring to the character table for the C4 point
group, we can see that the p, orbital now belongs to the a 1 representat ion and the p.
and p1 orbitals to the e representation. Thus in geing from
to C.., symmetry, the
triply degenerate p orbitals have been split into two sets. one nondegenerate and one
doubly degenerate. Similarly, the d orbitals are distributed among a larger number
or sets than was the case in the octahedral molecule. The e, level is split into two, a
ten
o.
72
S Sym melry oncl Gr oup The o r y
o,,
J,l,d,t _y l -
, -=----..,
d,, , . d:. 4Tl_l21{
b1
o, (d,t)
--- -- --u1 (d..,J
------ -------b,
------bz
(d-.)
- -
1 111
- - - - - - - b 1 (d1 ,J
----- o,---- - - -.,,
(p,J
" (p, )
(p,J
-a 11 ------o 1- -- - - -- a1 (1)
(b)
(<)
Fi11. 3.25 Central atom orbital S)'l'11lllelries and dqieneracies foro. A86 , C.., AB,, and
C1 AB. species.
b 1(d... _,.) and an a 1 (d.-). and the triply degenerate r 2, set is converted to t(d,.., dr-)
and b1(d..,). This loss of orbital degeneracy is a characteristic result of reducing the
symmetry of a molecule.
The symmetry will be lowered even fu n her by removing a second B atom to give
seesaw AB4 , a C1 structure (Fig. 3.25c). 19 The outcome is a complete loss of orbital
degeneracy. The char.tcter table shows the foll owing assignments: a 1(p,), b 1(p,), b2(p1 ),
a 1(d,,), a 2(d., ), b 1 (d...). and b 2(d1 , ) . The function x 1 - y 2 is not shown explicitly in the
Cz. character table because when x 1 and l are of the same symmetry, any linear
comb ination of the two will also have that symmetry. Note that although both the
cL,, and
orbitals transform as a 1 in this point group, they are not degenerate
because they do not tra nsform together. It would be a worthwhile exercise to confirm
that the s, p, and d orbitals do have the symmetry properties indicated in a C1
molecule. Keep in mind, in attempting such an exercise, that the signs of orbital lobes
are important.
The hybrid orbitals that are utilized by an atom in forming bonds and in accommodating its own outershell nonbonding electrons will have a spatial o rientation
consistent with the geometry of the molecule. Thus a tetrahedrdl molecule or ion,
such as CH 4 , MoO,;-, or CrO! - , requires four hybrid orbitals on the central atom
directed toward the vertices of a tetrahedron. The general procedure for determining
what atomic orbitals can be combined to form these hybrid orbitals st.a rts with the
. recognition that the hybrid orbitals will constitute a set or basis functions for a r-epre.
within the point group or the molecule. This representation, which will be
d,.,_,,
., Note in Fig. 3.2.S that the molecule has not only

B atom remo...S in aoina rr0111 AB, to AB4 bul
bas also betn turned rtlati"" to 1he oil system. nus wu done to bt tonsista'll with lhe convention rl
assisning the principal axis as z.
u ... of Point Group Srmmetry
r
fig. 3.26 A tetrahedral
All. species with vector.;
representing central atom
hybrid orbitals.
reducible. ca n be obtained by considering the effect of each symmetry operalion of

the poinl group on the hybrid orbitals. Once generated, the representation can be
factored into its irreducible componenls (page 62). At that point, we can obtain the
information we are seeking from the character table for the molecule, because atomic
orbitals which transform as these irreducible components will be the ones suitable
for combination into hybrid orbitals.
I n carrying out the procedure for a tetrahedral species, it is convenient to let
four vectors on the central atom represent the hybrid orbitals we wish to construct
(Fig. 3.26). Derivation of the reducible representation for these vectors involves performing on them, in turn, one symmetry operation from each class in the T 4 point
group. As in the analysis of vibrational modes presented earlier, only those vectors
that do not move will conlribute to the representation. Thus we can determ ine the
char.tcter for each symmetry operation we apply by simply counting the number of
vectors that remain stationary. The result for AB 4 is the reducible representation, r,:
r,:
3.27 The
ion
with vectors representing
Otbitals on platinum
suitable for out.ofplane
1r
t:
bonding.
73
6S4
Application of the reduction formula (Eq. 3.1) yields a1 and t 2 as the irreducible
components. Referring to the T 4 character table, we see that no orbitals are listed for
the totally symmetric a1 representation; however, recall that s orbitals are always in
this class. For the c2 case, there are two possible sets of degene>ate orbitals:
p1 ,
P: and d,1 , d,., d1 Thus the four hybrid orbitals of interest can be constructed from
either one sand three p orbitals, to give the familiar sp3 hybrid orbitals, or from an s
and three d orbitals to yield sd 3 hybrids. Viewed strictly as a symmetry question,
both are equally possible. To decide which mode of hybridization is most likely in a
given molecule or ion, orbital energies must be taken into account. For methane and
other cases involving carbon, the d orbitals lie too high in energy compared to the 2s
orbitals for significant mixing of the two to occur. However, for tetrahedr.tl species
involving transition metals, such as MnO; or CrO!-. there are d and s orbitals
similar enough in energy that the hybrid orbitals involved in bonding may be a mixture of sp3 and sd 3 It is important to understand that a charaaer table tells us only
what orbitals have the right symmetry to imeract; only energy considerations can
tell us whether in faa they do.
In deriving hybrit.l orbitals in the foregoing example. we assumed that these orbit
als were directed from the centml atom toward the atoms to which it is bound and
that the hybrid orbitals would overlap along the bond axes with appropriate orbitals
of the pendant atoms. fn other words, these hybrid orbitals will be involved in sigma
bond.s. The same basic approach that was applied to the construction of hybrid orbitals for the u bonds involving a central atom also can be used to select atomic
orbitals that are available for n bonding. As an example consider the square planar
ion,
Two types of n bonds between the platinum atom and each chlorine
atom are pOssible here:
with the two regions of overlap above and
below the plane of the ion, and "in-plane," having both overlap areas in the molecular
plane. Atomic orbitals on platinum that will be capable of participating in out-ofplane n bonding will be perpendicular to the plane of the ion and can be represented
by the vectors shown in Fig. 3.27. As before, a reducible representation may be obtained by carrying out the operations of the appropriate point group (D 4 ,) and, for
each operation, recording the number of vectors that remain unmoved:
r,:
2C4
0
2Ci
2q
3u4
74
S Symmetry orul Group Theory
Reduction of r, (Eq. 3.1) shows that it is composed of e,, nlM> and b2 The D...
character table reveals that no orbitals transform as bz., but that p, belongs to a 2
whiled,.. and d,. belong to e,. That these three orbitals on platinum are allowed by
symmetry to participate in out-of-plane n bonding is reasonable since they are all
oriented perpendicular to the plane of the ion (the xy plane). Selection of orbitals on
platinum suitable for in-plane 1t bonds is left as an exercise. (Hint: In choosing vecton>
to represent the suitable atomic orbitals, remember that the in-plane and out-of-plane
1t bonds will be perpendicular to each other and that the regions of overlap for the
former will be on each side of a bonding axis. Thus the in-plane vecton> should be
positioned perpendicular to the bonding axes.) 30
Crystallography31
The symmetry of crystals not only involves the individual point group symmetry of
the molecules composing the crystals, but also the translational symmetry of these
molecules in t he crystal. The latter is exemplified by a picket fence o r a stationary
row of ducks in a shooting gallery. If we turn on the mechanism so the ducks start
to move and then blink our eyes just right, tbe ducks appear motionless-the ducks
move the distance between them while we blink, and all ducks are identical. Under
these conditions we could not teU if the ducks were moving or no!, beclluse they
would appear identical after the change to the way they appeared before t he change.
If we think of the ducks as lattice points, a row of them like this is a one-dimensional
crystal. In a three-dimensional crystal, a stacked array of unit cells, the repeating
units of the system are like the row of dudes and display translational symmetry.
Determining the crystal structure of a compound by X-ray diffraction has become so important (and so routine)31 to the inorganic cbemist that nearly fifty per
cent of the papen; currently published in the journal Inorganic Chemistry include at
least one structure. What information is conveyed when we read that the solid state
sttuaure of a substance is monoclinic P2tft!! We can answer this question by 5tarting
with a few basics.
Diffraction pa tterns can be described in terms of three-dimensional arrays called
lattice points. lJ The simplest array of points from which a crystal can be created is
called a unit cell. In two dimensions, unit cells may be compared to tiles on a floor.
A unit cell will have one of seven basic shapes (the seven crystal systems). all con
structed from parallelepipeds with six sides in parallel puin;. They are defined ac
0
' All!wn-:
None; b,_: dqt l w: (p., P..
"Ladd. M. F. C. S,.,-tryln Moluksa.J Crystals: Wiky: New Yorit, 1989. Hyde. B. G.: Andcruon. S.
Inorganic Cr)5lal Stnu:tun<; WUey: New Yk. 1989.
u Then wu a lime when the collet:tion et data aftd rdOiution eta Ct)'StaiJo&rapllic suucture was a uuly
horrendous task, !be solution eta W\ale structure on.... b0f11 an accomplistunent worthy or" doctor.ll
dissert&Jion. Today, thllnlcs to automation and eompuocrization.
are rcscar<h oraanizaliom that
will cuannoce the n:solution eta structure CO<Otainin& a limited numba" et otoms in one v.cek 81 a
charge tlw, in tenns ettht costs or doina research, is rdaU\'Ciy unall. Fe. the ear1y days, sec w)'Cicoll,
R. w.
Posnjak. E. J. Alii. CJwm. Soc. 1921, 4J, 2192- 2309. For reprinu or lhls 11t1c1 rdaJed Jlll><n
toaelher with illuminalinc eommcnlal)', see CIG.uic:s In CoordinkM
l'tvr 3; Kauffrnon, G. B..
Ed.; Dover: New Yort.l911. Sec also Pa1Ain1o LIn Cr,-tttllogrupltyln North Ammc4; Md.odtlan. D.
Jr.: Glusl<..-. J. P Eds. : American
Auo<ialiun: New Yort. t9&l: Oq.lcr I.
, Brock. P. C.: l..iQpfeuer, C. E. J. CIJ,m.
1910. JJ. 552-4.
Cryotellogrophy
75
Tobie 3.6
Tho
vn cryotaloyalemo
Rel,.lono
between ......
Syotom
ond angle a of
unit coli
length and
e ngllootobo
,,...,....
o,b,c
a,p,y
Triclinic
a,b,c
Monoclinic
fJ
Orthomombic
a.b,c
Teuagona!"
II,C
lfold (identity or
Inversion) symmetry
only
2-fold axis (2 or 2)
in one direction only
(yaxis)
2fold aJCC$ in three
mutually perpendicular
directions
and Hexagonal
Cubic
a-P=%"
y= 120"
a,c
a= b= c
aefJsyc'J(J"
4-l'old axis alo118

z axis only
).fold or 6-fold axis alona
zuisonly
Four 3-fold axes eadl

Inclined al S4"44' 10 cdl
axes (I.e. parallel to
body-diagonals of unil
cell)
Wells. A. F. Stn.ctlltllllnorgonfc ClrrooWry, $th ed.; Oxford Univenity. Oxford, 11184.

Usod with pcnnisaion.
Certain lriaonal cryslals may also be rd=..S to rhombohodlal aus. the unil cell beir1J a
rt.ombobodron dellned by edt edac o and interuial qle o ( JOI90")
cording to the symmetry of the crys1al, which leads to certain relations between the
unit cell edges and angles for eadl system (Table 3.6). Although 1hese relations bet ween cell dimensions can be said to charac1erize a particu la r crystal system, lhey are
no1 1he criteria by which a cryslotllographer assigns a crys1al 10 one of the sys1ems
during a structure determination. Ra1her, t he assignmenl is mnde on the basis of the
wi1hin experimen
crystal's symmetry features. For example, n struewrc mny
tal error, to have all unit cell edges (o, b, and c) of different lenglh and all angles
(a. p, and y) equal to 90", su881CSting that it is orthorhombic. However, if i1 is found
10 possess only a single two-fold axis, it must be classified as monodinic.
Only fourteen space latt ices, called Bravais lan ices, arc possible for the seven
aystal systems (Fig. 3.28). Designations are P
I
F (face
center-ed), 3 C (face-cemercd in one set of races), a nd R (rhombohedral). Thus our
monoclinic smJCture n.tc belonss to the monoclinic aystaJ system and has a primitive Bravais lattice.
The internal molecular mucture of a unit cell may be complicated because a
lauice point may be occupied by a group of atoms or molecules, rather than a single
,. Further cliscuslioo d primitiYC.
al1<l bod.,.c:entcted buicQ will be lound in Ch:lptct 4.
76
3 Symmetry ond Group Theory
a p
r7
fi
I
I
I
,._
__ il:;p
a
t,
D
vb
Monoclinic
Tridlnic
Fig. 3.28 The fourteen Bravais lattices grouped according to the seven crystal systems.
77
fig. 3.29 A fO!!J" fold

. improper axis (4) opera1i0n.
I The 4 axis is perpendicular
= to the plane of the paper,
A1 and A,(+) are above
the plane, A1 and A4 ( - )
t are below. When a point
A, (x, y, z coordinates:
: +a. +b. +c) is rotated
; clockwise by 90", followed
; by inver.;ion, it becomes
: point A4 (-b, +a, -c).
In the same way, A2
becomes A,, A, beccrnes
; A1 and
becomes A3 .
atom. Consideration of these groupings and the overall symmetry which may arise
leads to thirty-two crystallographic point groups. All of the discussion of symmetry
and point groups until now has been in terms of the Schoenfties syscem that is preferred by spectroscopists and structural chemists who are primarily concerned with
the symmetry properties of isolated molecules. Crystallographer.; almost always work
with an equivalent but different system, the lmernacional syscem, also known as the
Hermann-Mauguin system. Some of the symmetry clements that can be present in
three-dimensional lattices are the same as we have seen in molecular point groups:
the center of symmetry (center of inversion), mirror planes (given the symbol m). and
simple n-fold rotational axes (designated by then value, n =I, 2, 3, 4, and 6). 35 A
mirror plane perpendicular to a principal axis is labeled nfm. In addition, there are
three other symmetry elements: axes of rotatory inversion, glide planes. and screw
axes.
In the Schoenflies system the improper axis is an axis of rotation-reAection (see
page 52). In the International system the a.tis of rmawry imersi011 (i'i) is one of
n-fold rotation followed by inversion (see Fig. 3.29).
A glide plane is a translation followed by a reflection in a plane parallel to the
U"dnslation axis. In the simplest case, consider a lattice with unit cell of length a along
the x axis (Fig. 3.30). Movement of a distance afl along the x axis, followed by reflection. accomplishes the symmetry operation. A glide plane is labeled a, b, or c
depending on the axis along which translation occurs. Additionally, glide operations
may occur along a face diagonal (an n glide) or along a body diagonal (a d glide). If
a glide plane is perpendicular to a principal or screw axis, it is shown as nfc, nfa, etc.
or n.fc. n,/b. etc.. respectively. Note that because of the reflection in the operation,
any chiral molecule will reflect as its enantiomcr of opposite chirality. For a glide
plane to be present in a crystal of a chiral compound, both enantiomers must exist
in the crystal, that is, it must be a racemic mixture.
Another symmetry element that may be present in a crystal is a screw axis
(identified by n 1) which combines the rotational symmetry of an axis with translation
along that axis. A simple two-fold (2 1 ) screw axis is shown in Fig. 3.31. In contrast
to the glide plane, only translation and rotation are involved in this operation, and
therefore a chiral molecule retains its particular handedness.
1-----u---.j
/
<f:r----;J
l/ / 17
Fig. 3.30 A glide-plane

operation. The molecule
moves a distance a/2 along
ahe x axis and then is
rcftected by the xy plane.
Noae that ahe chirality of
the molecule changes.
- - A - - - - - - - A - - - - - - - A - - xa.<is
II can be shown mathematically lhaJ

axes c:a.nnot appear in a truly periodic crystal or sinalc
wUI cdls repeating in $p01X. Neverthclcss.aome inlercsling "quasicryslals" have r=ntly been cliscoveml
lhat have unusual symmetry properties. Sec Problem 3.39.
78
3 Symmetry and
GtOUIJ
Theory
Fig. 3.31 A saew-axis (2 1)

operation. The molecule
moves a distrulee a/2 along
the x axis while undergoing

a C1 rotation. Noce thac
the chirality of the molecule
does not change.
An equivalence table of che 32 crystallographic poinc groups in the two systems
is given in Table 3.7.36 The complete set of symmetry operacions for a crystal is
known as its space group. There are 230 possible space groups for three-dimensional
cryscals. Note l.hac whereas chere is an infinity of possible point groups, the number
of space groups, despite che addicion of cranslacional symmetry, is rigorously limited
to 230. For each structure worked out by the crystallographer. an assignment to one
of these possible space groups is essentiaL Fortunately, this task is made easier by
Tobie 3.7
Comparison of SdloenRies oncllntemationol nolo IiGas lor tile thirty-two
Tridinic
Monoclinic
c,
c,
Trigonal
2/m
c.
c,.
222
D,
cl.
mm2
mmm
Tetragonal
Dv.
c.
c
D4
c
42m
Du
o..
4/mmm
16 For a
32
3m
c..,
o,.
6/m
6mm
c..
6/mmm
23
m3
432
T
0
m3m
o.
6m2
Cubic
c,
D,
c.
clio
c..
6
622
s4
4/m
422
4mm
c,
lm
Hexagonal
Onhorhombic
SchoOftllies
cl
point groups
Hwmann-Mouguln
Scho-les
43m
D:u.
r.
r.
flow chan of the 32 cryscallogruphic poinl grOup$ in the lnlemaclonals)'Siem that is analogous
to Fie. 3.16 ror che Schoennies sysccm, see Br<n<:OMn. G. L J. Chtm. E</llc. 1987.64. 216.
Cryol oll l"hy
79
the c:onspicuous evidence left by elements of tr.lnslational symmetry: All fonns of

tr.lnslational symmetry, including lauicc centering, create empty spaces in the diffraction pattern called ksystematic'' absences.
We can now complete ou r answer to the question, MWhat information is conveyed when we read that the crystal structure of a substance is monoclinic P2 dc?"
The structure belongs to the monoclinic crystal system and has a primitive Bravais
lattice. It also possesses a two-fold screw nxis and a glide plane perpendicular to it
The existence of t hese two elements of symmetry requires t hat there also be a center
of inversion. The Iauer is not specifically included in the space group no ta tion as it
would be redundant.
Frgure 3.32 illustrates the unit cell of
a compound lhat
crystalliu:s in the monoclinic space group P7. 1/c. In addition to rhe identity element,
it exhibits two two-fold screw axes. two c gl ide planes. and an inversion center. As an
aid in the identification of these elements, the four molecules of the unit cell are
(II)
tbl
Fig. 3.32 Ia) the. molecular Slruclure or Ooi,CC0).,(14,-CC,.F.), consisting or :t tri:lnsJe of
osmium aroms cippcd by 1he
grotlllto rorm a 11'UlnguJar pyramid. (b) S1ereoview
or unit cell of Ooil(COM14CC..F,1. The compound crysealil.es in 1he monoclinic space
sroup P2,/c wi1h cell paramc:ters o - 1212.7( 10) pm, b- 938.6(5) pm. c !829.8(151 pm.
P 98.92(6r. The center or inversion is indicaled by " dot in 1he ccn1er or 1he unit cell, and
the two two-rokl screw axes arc pcrpcndiwlar to the plane o( lhe paper ond are
with the symbol f . Two glide planes perpendicular to the screw axes in the :xy plane (paraUet
with the pane or the paper) are not indialtcd but arc round at distances or onc-rOU<th and
three-fOurths unit ccU depth. Note that a. b. and c do no oornspond exoctly to x, y. and z
becluse one o( the three anaJcs or a monoclinic Slructure is unequal to 90". The ftuorine
111ams have been omitted ror clarity. [Modilic:d rrom Had}Bagheri, N.; S1rickbnd. D.
Wllsoo, S. R.; Shapley, J. R. J.
CNm. 1991 ,410, 231 - 239; Courtesy oi"S. R.
Wilson and C L Stem.)
10
3 SymmeJry and Gf"oup Theery
Table 3.8
Symmetry relations belwHn
the four molecules shown
in the unit cell of
os3 (C0)9 (p3 -CC.F5 )
depict.d in Fig. 3.32
3
2 1 screW
. cglide -.
2 1 screw
inversion
identity '
inversion
identity
numbered and are related by symmetry as shown in Table 3.8. The identity operation. of
course.leaves the positions oft he molecules unchanged . The inversion center lies at the
center of the unit cell, and it interchanges I with 2, and 3 with 4. Two screw axes are
found perpendicular to the xz plane and are indicated in the figure. Note that they
do not pass through the center of the unit cell but are found at half the x distance
and one-fourth the z distance, and at half the x distance and three-fourths the z
distance.. The first of these transforms 1 into 3, and at the same time 2 and 4 are
moved to adjacent unit cells. The second screw axis, related to the first by the inversion center (and therefore rotated opposite that of the first screw axis). takes 2 into 4,
while transforming 1 and 3 into neighboring cells. Glide planes are xz planes and are
at one-fourth and three-fourths the y distance. The first transforms 2 into 3 (with 1
and 4 being reflected into adjacent unit cells). and the latter transforms l into 4 (with
2 and 3 being reflected out of the unit cell).
Although P2tfc is one of the simplest space groups, it is also one of the most
common because complicated molecules tend to crystallize in patterns of low symmetry. The above example illustrates the principal difference between point groups
and space groups. The former requires that some point remain unmoved during the
symmetry operation, while the latter does not have that restriction.
Disorder
In order to keep the section on crystallography relatively short, this discussion has
not included the theoretical basis for X-ray diffraction. However from other courses
you are probably aware of Bragg's Law and the diffraction of X rays by regularly
spaced atoms comparable to the diffraction of visible light on phonograph records or
compact disks. Thus one necessity for obtaining X-ray diffraction data is the presence
of crystalline material ( regularly spaced atoms). Amorphous materials do not have
the regular spacing necessary for diffraction. However, even seemingly pure crystals
may be subtle mixtures of two related compounds leading to erroneous results. And
since crystallization is a kinetic process, even an otherwise pure compound may not
crystallize in the single thermodynamically most favorable perfect crystal. There may
be a statistical disorder with most of the unit cells having molecules lined up in the
preferred conformation but a fraction of the unit cells with molecules in a different
conformation of slightly higher energy. Since the X-ray diffraction results are summed
over all of the unit cells, the resultant structure will exhibit this disorder.
[fa molecule has a high rotational symmetry except for a small symmetry breaking
atom or group (R), the molecule may pack in any of n-fold ways with R having no
effect on the packing, but showing up as 1/n Rat each of then possible posi1ions.37
For example, a model compound for studying the interaction or the dioxygen mole-
, Obviously, if R is large enouah 10 alfect the pecking of abe molecule in lhe crysaal then tbe poulbilily
of routional di5or-der does not cxlsL
Cryatellogrophy
11
cule with the heme group (FeN4 C 20) in hemoglobin has four-fold rotational disorder
of the distal oxygen atom, and so that atom,
0 2 (Note: In crystallographic
structures the subscript refers to ..oxygen number two"; 0 2 does not refer to the
dioxygen molecule as a whole), shows up as four ..one-quarter atoms":
In the same way the N-methylimidazole ligand (the group

the iron atom)
shows a two-fold disorder with respect to where the methyl group is located. The
model compound has pseudo-four-fold symmetry and the rotational disorder can
have no effect on the molecular packing. This is espo:ciaUy evident looking at the 0 2
buried in the molecule; see Fig. 19.4 for the complete structure.
In some cases, such as the above, the confusion is minimal, ahhough the presence
of fractional atoms may
startling the first time one encounters them. In other
cases, the problem may
considerably more serious. Perhaps the ..classic" case in
inorganic chemistry was the difficulty in the resolution of the structure of Fe 3(COI 12.
Becuuse of disorder in the solill. a "Star of Davill" of six lt111j utoms was founll, as
shown
The structure of Fe 3(C0) 12 is an example in which the disordering occurs about a

center of inversion, a symmetry-related dlsorder. 39 We have seen that the positions
11
L.
Rundle, R. E. J. CMm. Phys. 1951,16, 17SI-17S2.
Whether a molecule is aC(ually dynamically moving in the crystal or merdy statistically

among several possible positions is a moot poiru as Car as X-ray crystallography is concerned since rhe
interaction lime of lhe X ray with the crystal is of the order or 10" 10 s, faster than atomic movements.
In the case r:llriiron dodecacarbonyl we have other evidence {see Chaplet' IS) ror believing that the
io'on atoms are movins. But they need noe-che disorder arises from lbe location oC a moleetAe without
a c:mter of aymmetl)' [Fc.(C0)1 on a symmetry element ol tbe unit cell (the c:mter cl inversion).
12
S Sy"'mehy entl Group Theory
of atoms in unit cells are related by symmetry elements. If a molecule lies on a fixed
symmeuy element (center of inversion, rotational axis, mirror plane) and does not
icsdf possess thac S}'tlmelry element, there will be a superposllion of images. Usually
in such a situation, the overall shape of the molecule and distribution of polar bonds
will be similar for the two (or more) disordered fragments. This is the case in triiron
dodecacarbonyl (the complete structure is illustrated in Fig. IS.7). The two possible
orientations of the "iron triangle" are superimposed to give the hexagonal arrangement observed.
Due to the superposition of two inversionally related half molecules in Fe,(C0), 1
the determination of the arrangement of the carbonyl groups proved a difficult task.
In fact, nearly 17 years elapsed before it was successfully solved by a process or
computer simulation and modeling,..,
A current example o( a solid that is disordered at room temperature is buckminsterfullerene. Until re(ently, only two allotropes of carbon were known: diamond
and graphite. However, on the basis of ions detected in a mass spectrometer with
mle = 720, a C60 molecule was hypothesi:z.ed.4 1 Now this third allotrope. C 60, has
been isolated from the vaporization products or graphite. One heats carbon rods
in an inert atmosphere or helium or :u-gon, and extracts the soot that forms with
bemcne...1 The proposed structure is anlllogous to a socoerball" with bonds along
the seams and carbon atoms at the junctures or the seams (Fig.
The name
W1IS suggested because of a fancied likeness to a geodesic
dome. This was quickly reduced by the waggish to "buckyball".
T he synthesis of macroscopic amounts of buckyball led to the study of many
interesting propert.ies of this molecule which continue unabated 35 this book goes to
press.'" The C60 molecule is near1y spherical. and while the molecules themselves
pack nicely in a cubic closest packed structure, each molewle has essentially the free
rotation of a ball bearing, and because of this disorder the structure could not be
determined at room temperature.4 ' Being nearty spherical and lacking bond polarities
.. Couon. F.
Troup. J. M. J. Am Chtm. Soc. 1974.96. 4tSS -4 tS9. See also Wei, C. H.:
L F.
J. Am. Chtm. Soc. 1969, 9/, IJSI- 1361. For lunhtr discUlllion d Ihis problem togelhtr wilh ollcmaaivc
apP<onchts to ahe mucturJI solullon.... Chapler 1S.
Kroao. H. W.: Hcuth. J. R.: O'Dricn. S. C.: Curt. R. Smalley, R. E. NOl!Ut t98S, JIB, t62.
Kriiascluner. W.: Lamb, L 0.: Fosliropouka. K.: Huflmen. 0 . NU11.rt t990, Nl, 3S4-JS8. See olso
Allcm:md.
Koch. A:. Wudl, F Rubin. Y Dicclerich. F Alvarc-z. M.
Anz. S. J.: WhciiCil,
R. L. J. Am. Chtm. Soc. t99 1. 1/J, 10.50-tOSI. With rqvd lo lhe QUIion
in Chupler I conccminc lhe
dlemistry paf..-.ncd by
blldcminslerfiAietc,.. ""Y have been synlhesi%0\1
quice early :uul deposilccl in the SOOI on cave waas! tn lace. buminQ p<O<esses hold prcmi'"' lor lhe
lo<Jescole
or IUIIcttnes.
Or a lootboll in 1he European ond Soulh
scnoe
.. M>lr uJ.Irrl in proqf. The entire Mlll'th 1991 issue or Mrutmrl r>{ Cltmti<'ul RtJMn is 11<-<d 10
fullcrcnc:s.
Pttre.SlJI:IIimod l:luctminskrl'ullcrdlcconcknsesino
cullicdoscst padcccl)
slruclurc. Complic::Jlions moy occur thro.,.h the presm ol other lulkra>e impurilia or ct,stoUiution
l..cwU. T.
Loren, S.
Meyer. A:.
J. 1L:
lrom a wricly or solvcnu. See Hawkins, J.
SaybUy,
Hollander, F. J . J. Chtm.Soc.. C'-. ComoiiJft. 1991.
Gtlo.
Karuur.1, N.;
Godd.atd, W. A., Ill NIIIWt 1991, J.SI, 464-467.
Cryotollo grophy
13
(a)
(b)
Rg. 3.33 Comparison of tal n scx:cer hll And (b) slruc:lure of I he C,,. molecule.
!Courtesy of D. E. Weeks. !!. und W. G. Harter. I
that might contribule 10 Janice energy, lhe molecules nre almos1 complelely rolalionally disordered, though thei r cemroids nrc fixed in space.46
The problem or rotational disorder was solved by making nn osmyl deriv-.nive
or buckyball. Osmic acid, Oso will add ncross double bonds:
(3.2)
.. The ocar1y i>otropic rotalion is elcarty sllown by ''C NMR

C.s.; Dom, H. C; Salem, J. R.; Bdhunt, D.S.
199Z. 1SS, IZJS- 12.3&.
R.
14
1 Sy.,.,elry
entl G r oup Theory
F;g. 3.34 ORTEP drawing
of the one-to-one
adduct Coso(OsOJ
(4-t-Bu-pyridineh showing
the! relationship of the
osmyl unit with the
cluster. [From Hawkins,
caroon
1.
T.
Meyer, A.; Lewis,
Loren, S.; Hollander,

F. J. Scierv:e 1991, 252,
312- 313. Reproduced with
pennission.)
The presence of one or more bis{4-r- butylpyridine)osmyl groups provides Mhandles"

to break the pseudospherical symmetry of the C60 molecules and anchor them in
the crystal. The X-ray crystal structure of the one-to-one adduct was readily accomplished. This allowed the authors to say:
"The crystal structure [Fig. 3.34] confirms the soccer ball-like arrangement of
carbon atoms in C 60 by clearly showing the 32 faces of the carbon cluster composed of 20 six-membered rings fused with 12 five-membered rings. No two fivemembered rings a re fused to.sether, and each six-membered ring is fused to alternating
six- and five-membered rings. The 0 - 0s- 0 unit has added across a six-six ring
fusion ......,
A phase cha.nge for C60 occurs at 249 K (face-centered cubic to simple cubic).
phase, unlike that at room temperature, is ordered and thus
crystallographers have been able to obtain a crystal structure of the underivatized
product. 48 In addition, the gas-phase structure has been determined by electron diffraction.49 The gas-phase cartx>n-carbon bond lengths are 140.1 pm for the bond
The
Hawltint, J.
A; Lewis, T. A; Loten, S,; Holludcr, F. J. Sdcnct l991. 1Sl. 3t2-3Jl.

l,l.1J4, 40&-4t0. David, W. I. F.; ltlbcnon.
R. M. :Pobahcwmon. J. C.: PRssidts. K.; Daris. T. J. S.; Har<, J . P.; Krolo, H.
R. ; walloa.
D. R. M. Norur, m1. J, 147-149. BOqi. H.8.; Blanc, E.; Schwatunbadl. D.; Liu. S.; Lu. Y.-J.;
Jeawes, M. M.; lben. J. A. AJtrrw. Clwm. Int. 4. U.l. m1. Jl ,
H<dbera, K..; Hedber&, L.; 8elhuDc, D. S,; Browa. C A; Doni. H. C; Johnsoa, R. D.; DeVria, M.
1991, 1S4, 41Q-412.
"'Uu. S.; Lu. Y.-J; " - M. M.; lbtn, J. A.
Problems
85
fusing six-membered rings and 145.8 prn for the bond fusing five- and six-membered
rings.
Buckminsterfullerene has a high electron affinity. Treatment with up to six moles
of an alkali metal such as potassium or rubidium gives products
(3.3)
which show metallic conductivity. If only three moles of potassium or rubidium are
allowed to react, the products consist of K3 C60 and Rb3 C60 which become superconducting at temperatures below 18 K and 30 K, respectively. so These compounds
have a face-centered cubic cryolite structure with a closest-packed array of
anions with M+ ions in the tetrahedral and octahed ral holes (see Chapter 4). At
present it does not appear that these superconductors will prove competitive with the
cuprate high-temperature superconductors (Chapter 7) because of their much lower
critical temperature and the fact that they are quite susceptible to oxidation.
Buckminsterfullerene. C 60 , appears to be the first of a large number of allotropic
fullerenes: C70 is already fairly weD known-it probably has the shape of a rugby
ball-and other c. molecules with n = 76, 84, 90, 94 have been isolated. Even larger
molecules with n equal to 240 and even 540 have been suggested st
3.1 As9gn the molecules in Figs. 3.2, 3.4, and 3.7 to their appropriate point groups.
3.2 Assign the molecules in Figs. 3.S, 3.6, and 3.8
10
their appropriate point groups.
3.3 Assign the following molecules to their appropriate point groups.

L
c:yc:Jopropane
._ B,H6
g. BF1
b. S02
e. P.
b. PH 1
H
c. CO 2
f. 0 1 C= C=CC1 2
i. O:SCI:
I
0- B
0- H
'oI
H
3.4 Assign the following to their npproprinte poinc groups.
a. tris<oxal:uo)c;hromium(JII)
b. tris(c:arbonato)cobalt(IJI)
c. tris(glyc:inato)coballllll)
o., T4 , C 1, C, and C,symmetries were assigned in the text by inspec:tion.

Take the molecules given as illustrations of these symmetries (Figs. 3.10 and 3.11) and
run them through the flowchart (Fig. 3.16) to assign their proper point groups.
3.6 Although most molecules in point groups ' 0., T., C1, C,, and C, may be assigned by
inspeaion, some appear unusual. Consider the cubic symmetry of cubane, C1 H1 . To
3.5 Groups with I.,
"'f1cmin&
R. M.; Rami=. A.
Rosscinsky, M. J.; Murphy, D. W.; Hldclon, R. C; Zahunk. S. M;
Malthija, A. V.
1!191, JJl. 781.
" Diederich. F.; Enl. ll; Rubin. Y.; Whencn, R. L.; Bcdc. ll; Alvan:%. M.; Am. $.; Scnsharma. D.; Wudl,
F.; Khanan, K. C; Koc:b. A. Sdttct l!I91.1J2, 548; Kroto, H.
Appl.
1990, 62, 407-4tS.
16
3 Sy mme try Grau p The ory
what point group does it belong? Consider the pentagonal dodecahedron. (For a model,
see Appendix H.) To what point group does it belong'!
H
3.7 Find the symmelr)' clements. if any, in the objects shown in Fig. 3.1.
3.8 In the discussion of crystallography, translational symmetry was bl:ened to moving ducks
and blinking eyes. Extend this discussion to the action of a strobe light blinking t times
pu second relative to the foUowins.
L
ducks moving with a certain linear velocity
b. a spoked wbeel spinning at a a:rlain angular velocity
c.., symmetry rather than c..? (See Fi&- 6.4).
3.9 Why does SF. have
3.10 Find all of the symmd ty elements in an oetahedron.

3.11 T ris(2-aminodhoxo)coball(lll) (Fig. 3.12b) was assigned C 1 symmetry, butlhe methylene
groups of the ligand were not drawn out explicitly. Ooes consideration of these groups
change the symmetry? Discuss.
3.12 Gauc.loeH,0 2 has C 2 symmetry. What are the symmetries cl the eclipsed (cis) oonforma
tion and the anti (trans) conformation?
3.13 On page 64the afGUmem is made that a molecule with a center of symmetry, i, cannot have
a molecular dipole moment. Prove this Sll/1\e rule using a molecule with a center or
symmetry and summing up the individwll bond moments.
3.14 Meso molecules such as R,S-1,2-dichloro-1,2-difluoroethane are usually cited as achirnl
because they possess o mirror plane (when in the perfectly eclipsed conformer, n stipulation that is often
What is the symmetry of this conformer? In other con
formations? Discuss why meso molecules show no optical aaivity.
3.15 Which of the following molecules will have dipole moments?
CI - F
S = C= S
F- 0
3.16 What are the symmetries of the normal modes or vibration of these molecules?
F-0
Problems
87
3.17 Unlike the water molecule, carbon dioxide has no dipole moment. How is it possible for
any of its vibrational modes to be infrared active?
3.18 Sketch the normal
modes for CO! und indicate which you expect to be
infrared or Raman active, or both.
3.19 A hydrogen bond consists of a positive hydrogen betwew two very negative
aaoms. One of the strongest hydrogen bonds known, the HFi" ion. will be discussed in
Chapter 8. Possible arrangements of the atoms in [FHFJ - ion are a) linear or b) bent,
wilh either: i)equaL [F---H---FJ-, or ii) unequaL [F-H----F]-, bond lengths. The fundamental vibrational absorption frequencies (in em - ) of the hydrogen difluoride anion
and the dcutero-subslituted Mion are as liSted below. 01
HF2
DFi
Activiay
ISSOcm-
1200cm-t
1140cm-
615 em-
61S em-
IR
IR
Raman
860cm-
Suggesa the structure of the hydrogen difluoride ion. Explain your reasoning,
3.20 Proceeding through an analysis analogous to that described in this chapter for BCI3 ,
derive the irreducible representations for the normal vibrations of XeF (Fig. 3.24) and
determine which are IR active. which are Raman active, and which are neither.
3.21 Determine the number of fundamental vibrations that would be expected for XeF4 if it
were tetrahedral. How many of these would be infrared or Raman active? Compare Ill=
resuiL' as well as those obtained from Problem 3.20 with the cxpcrimcnhll duta given on
Plii:C 70. und give as muny reasons liS pos. ible for eliminating the
structure.
3.22 Determine the irreducible representntion of each of the fundamental vi brntions of truns(Pt02Br1]1- (a square planar structure/. Which nre IR active?
3.23 Use your answer lo Problem 3.22 and Footnote 28 to determine whether the first overtone of any of the fundamental vibrations ofrralfs[PtCI1 Br2) 2 - will be IR aeaive.
3.24 How many absorptions would you expect to see in the infrared spectrum of the T-shaped
OF, molecule?
3.25 Infrared and Raman spectro or crystalline barium rhodiwnate have been reported."
From an inspection or ahe data, the author oonduded that the rhodizonate ion, C60i-,
(Fig. 16.35) probubly hots D6 symmetry. Examine the daln below (frequency in em -t )
un<.l explain this conclusion.
IS2(1R)
27S(IRJ
380(1RI
1071 (IR)
1278(1R)
1305(1R)
450(Rama n)
548(Roman)
1551 (Raman)
1475(1R)
3.26 Bromine pentafluoride reacts with lithium nitrate to produce BrONO,:

lliNO,
+ BrF,
3LiF + Br0N0 2 + 2FNO, + Oz
(3.4)
Draw the struct\ll'e t'K the planar BrONO, molecule an<! dclermine the irreducible representations for it< vibrationnl modes. Which mocles arc IR active an<.l which unc. ure
Rum"n active'! (Wilson. W. W. : Chrite. K. 0.
Chem. t987. 16. 1573.1
'""'II
"Harris, D.
Bertolucci, M. D. Syrrtmnry md
. " Bailey, R. T. J. CMm. Soc., Chtm. Ccmmun. t970, 322.
Dover: New YC<k, 1989; p 160
88
3 Sy "'motry
Gro up Thoary
3.Z7 F ig. 3.25 shows removal of 8 from octahedral A86 to give square pyramidal AB, and
loss or a second 8 to give seesaw A84 Suppose that instead of the geometries shown,
the AB, rearranged to give a trigonal bipyramidal struciUre and A84 assumed a square
planar shape. What orbital symmetries and degeneracies would occur for these two cases?
3.28 Consider the following AB. molecules and determine the symmetries and degeneracies
of the s. p, and d orbitals on A in each.
b. A84 (square plane)
a. A88 (cube)
A 8 3 (trigonal pyramid)
e. A83 (T-shape)
d. A83 (trigonal plunc)

f. AB4
plane)
3.29 For each of the following molecules. determine what atomic orbitals on the central atom
are allowed by symmetry to be used in the construction of sigma hybrid orbitals.
a. NH3 (trigonal pyramid)
b. BF3 (trigonal plane)

d. PFs (trigonal bipyramid)
of A86 Five
potential S(rocturcs were considered, belonging to point groups 0 1 , D3 ,. Dt.k> D- alld
D>J. Spectroscopic studies led to the conclusion that the p orbitols originating on A in the
complex were completely nondegenerate. Sketch a structur:al formula that is consistent
with each of the five point group assignments and decide which structures can be dimi
nated on the basis of the experimental results.
J.3() A chemist isolated an unknown transition metal complex with a formula
3.31 What atomic orbitals on carbon in the planar COl- anion could be used (on the basis
or symmetry) to construct in-plnne and out-of-plane ll bonds? First answer the question
by tbink.ing about the orientations or the orbitals relative to the geometry or the ion;
then answer it by using reducible representations and the appropriate character table.
3.32 What is the symmetry of buckminsterfullerene? 34 Do you
it to be chiral? To have
a dipole moment? To be soluble in benzene? Buckminsterfullerene was named after R.
Buckminster Fuller, who became best known for his popularization of the geodesic dome.
Is a geodesic dome the same as a segment or buckminsterfullerene? What is the symmetry
of the bis('k-butylpyridine)osmyl derivative of buckminsterfullerene (Fig. 3.34)? Do you
it to be chiral? To have a dipole moment? To be soluble in benzene?
3.33 How many
13C
NM R signals do you
to see for C 60? How many for C, 0 ?
3.34 look up carborrcarbon bond lengths (single, double, and aromatic) in an organic chem
istry textbook and compare with the bond lengths in buckyball. What can you conclude
about the bonding in buckyball?
3.35 D epending upon the conditions, reactant ratios, etc, the products of Eq. 3.2 consist of(l)
a toluene-soluble fraction lhat gives a single, sharp chromatographic peak for a material
that analyzes C 600 4 0s(NC,l{.C.H 9), and yields the structure shown in Fig. 3.34, and
(2) a precipitate that analy:tes as Ct>OIO.Os<NCsH 4 C4 H 9 hh What is the
or a
single bis(4-t-butylpyridine)Dsmyl derivative (I) o( buckminsterfullerene? When (2) is
analy:ted chromatographically, live peaks are observed. Discuss.
3.36 It has been suggested that if the potassium (or rvbidium) a toms in the M 3C 60 superconductors could somehow be placed inside the buckyballs, they would be protected,
and then these superconducton; would not be susceptible to oxidation. Commenl
,.. In answering this question. you may lind i1 userul to budd moclct or buc:l<ybaiL See Vinal. J. J. J.
Clwn. dMc. 1989, 66, 282.
Problems
89
Fig. 3.35 Scanning

electron micrograph of a
cluster of quasicrystals of
Al6Culi,. [Courtesy of
B. Dubost and P. Sainfort,
Pechiney, France.]
3.37 What are the symmetries of the following?
a. a baseball
b. a baseball glove
c. a baseball bat
d. a volleyball
e. a hoclcey puck
f. a soccerball
g. a football
b. a seamless rubber ball
3.38 Construct models of the teuahedron, the octahedron (b01h with and without
representing chelate rings), and the icosahedron (Appendilt H). Find and mark
as many symmetry elements as yOu can.
3.39 Recently
having the shape of a triaoomahedron have been discovered in
specially prepared alloys of aluminum and other meaals. A triacontahedron is a regular
polyhedron with 30 identical, di<lmond-shaped faces (Fig, 3.3S). Quasicrystals seemingly
defy the rules or symmetry that do not allow a periodic saructure having unit ceds wiah
five-fold symmetry." What is the symmetry of a triacontahedron? Can you make a model
or it similar to the polyhedra giYCtl in Appendix H?
3.40 F igures 3.36 and 3.37 illusirate two woodcuts by artist Maurits Escher. What symmetry
elements can you find?' 6
3.41 Among the thineen possible monoclinic space groups are P2 1, P2 1/m, and P2tft:. Com-
pare these space groups by listing the symmetry elements for each.
3.42 OOen hydrogen moms e>nnot be locatccl crystullosruphically if ahere are heavy :uoms
present. In a study uf H)F;SO:,Fj1, the hydrogen bonded cation was found tO have a
saructure or either:
\
[
/H
F-H-F
]+
]+
[\F---H---F
\
H
(a)
(b)
ss Horgan. J. Scimce 1990. 247, 1020-1022

.. For a compreberuive volume comparinssymmeuy in art. mwic:, cbemisuy, and other human mcleavon,
sec: Sylftmttry. Unifying Hwrum UntkrSlDtldlng;
l, Ed.; Persamon: New Yorlt, 1986.
tO
3 Symmetry Otuf Group Th e olfy
3.36 " Buuertty, &1.

Bird. 8," a woodcut
by Maurits Escher.
[Reproduced with
permission; Copyright 1990
M. C Escher c/o Conlon
Fig. 3.37 -Deplh," a

woodcu1 by Maurils
Escher. [Reproduced with
permission: Copyrighl 1990
M C. Escher cfo Cordon
An- &am-Holland.J
l'foblemr
91
1lle authofs SUited that ''(The structure) has space sroup Pl. Owina to the stronaJy scatterina Sb atoms. the H ntoms . could not be definitely locatized .. The H,F;ion ..
is located on a symmetry cerue.- of the space group and therefore has (a or b? Choose
one.] conformation."" Discuss how the correct conformation. a or b. can be chosen by
symmetry argumerus even if the hydrogen atoms cannot be located
3.43 Fig. 3.38 is a stereoview of the unit cell or Fe(CO)..It71-PPh 2 CH2 CH2 PPh,) which crysUillizes in the monoclinic space group P2 1fc. Find the symmetry elements of the unit
celt [ Hint: Find three easily recognized atoms in the Fe(CO).(I7 1 -PPh 1 CH 2CH 2 PPh,J
molecule and conoea corresponding atoms in the four molecules in the unit cell with tie
lines. Think about the relation of the intersection of these tie lines and the symmetry
elemerus.]
F'og. 3.38 Stereoview of the unit cell of fctC01.4'1' Ph:PCH 1CH1 PPh:1- (From Kcitcr.
R. L.; Rhein&old. A. L.; Hamel'lil<i, J. J.: Casde. C. K. Orxunmll<'lttlli<-s 1983. ! .
161S-1639. Reproduced with
3M The usual procedure for idemifyina chirnl molecules is to look for a mirror plane lu S11.
However. a ce ruer of inversion li S,) also produces an achiral molecule ls<e R .S l.1
of an S, axis wiD alsu
dimethyJ.I.!-diphenyldiphophine disulfide: Fig. 3.31. 1lle
re ult in an ochiral molccuk. Is the
zinc(IJ) ion I Fig. 3.391 chirul? What about the hiSIS.S '-2.3diaminooutunctzincllll ion'!
Fig. 3.39 The

IR.R'-2.3-<IiaminobubncJ.
IS.S'-2.3-<Iiaminubnelzinc(JI) ion.
3.45 Look at the drawings accompanying Problem 3.6. Is it possible to superimpose the cube
on the dodecahedron? Castleman and coworkers.. have recently detected a cation with
m/e 528, identified as
ft is believed that tile titanium atoms form a cube with
the addition of twelve carbon atoms to complete a pentagonal dodecahedron. Draw the
proposed strucaure. What is itS point group symmetry?
n.c:,.
Mootz.
'"Guo.
Banmann. K. /uofltw. Cltmt. llll. EJ.

1!188.17. 391.
Kerns. K. P.; Castleman. A. W, Jr. Sdence 199:Z..ZJS. t411 - t.t2.
Chap
er
4
Bonding Models in
I norga ni c Chern i stry:
1. Ionic Compounds
Structure and bonding lie at the heart of modem inorganic chemistry. It is not too
much to say that the renaissance of inorganic chemistry following World War II was
concurrent with the development of a myriad of spectroscopic methods of structure
determination. Methods of rationalizing and predicting structures soon followed. In
this and following chapters we shall encounter methods of explaining and predicting
the bonding in a variety of compounds.
The Ionic Bond
Although there is no sharp boundary between ionic bonding and covalent bonding.
it is convenient to consider each of these as a separate entity before attempting to
discuss molecules and lattices, in which both are important. Furthermore, because
the purely ionic bond may be described with a simple electrostatic model, it is advantageous to discuss it first. The simplicity of the electrostatic.model has caused
chemists to think of many solids os systems of ions. We sholl see that this view needs
some modification, and there are, of course, many solids, ranging from diamond to
metols, which require alternative theories of bonding.
Properties of Ionic
Substances
Several properties distinguish ionic compounds from covalent compounds. These

may be related rather simply to the crystal structure of ionic compounds, namely,
a lattice composed of positive and negative ions in such a way that the attractive
forces between oppositely charged ions are maximized and the repulsive forces between ions of the same charge are minimized. Before discussing some of the possible
geometries, a few simple properties of ionic compounds may be mentioned:'
I. Ionic compounds tend to have very low electrical conductivities as solids but
conduct electricity quite well when molten. This conductivity is attributed to
the presence of ions, atoms charged either positively or negatively, which are
free to move under the influence of an electric field. In the solid, the ions are
92
' Some very iDICR$tina ionic compounds prove 10 be exceptions 10 these rules. They are discu.ued in
Chapter 7.
n e Io ni c loncf
93
bound tightly in the lattice and are not free to migrate and carry electrical
currenl It should be no ted that we have no absolute proof of the existence
of ions in solid sodium chloride, for example, though our best evidence will
be discussed later in th is chapter (pages 111- 113). The fact that ions are found
when sodium chloride is melted or dissolved in water does not prove that they
existed in the solid crystal However, their existence in the solid is usually
assumed, since the properties of these materials may readily be interpreted in
terms of electrostatic attractions.
2 Ionic compounds tend to have high melting points. Ionic bonds usually are
quite strong and they a re omnidirectional. The second point is quite important,
since ignoring it could lead one to conclude that ionic bonding was much
stronger than covalent bonding-which is not the case. We shall see that substances containing strong. multidireCtional covalent bonds, such as diamond,
also have very high me lting points. The high melting point of sodium chloride,
for example, results from the strong electrostatic attractions between the sodium cations and the chloride anions, and from the lattice structure, in which
each sodium ion attracts six chloride ions. each of which in turn attracts six
sodium ions, etc.. throughout the crystal. The relation between bonding, structure, and the physical properties of substances will be discussed a t greater
length in Chapter 8.
3. Ionic compounds usually arc very hard but brittle substances. The hardness of
ionic substances follows natu111IIy from the argument presented above, except
in this case we are relating the multivalent attractions between the ions with
mecluutica/ separation rather than separation through thermal energy. The
tendency toward brittleness resulls from the nature of ionic bonding. If one
can apply sufficient force to displace the ions slightly
the length of
half of the unit cell in NaQ), the formerly attractive forces become repulsive
as anion-anion and cation-cation contacts oocur; hence the crystal fties apart.
This accounts for the well-known cleavage properties o f many minerals.
4. Ionic compounds are often soluble in polar solvents with high permittivities
(dielectric constan ts). The energy o f interaction of two charged panicles is
given by
qq-
E = 4nrt:
(4.1)
where q and q- arc the charges, r is the distance of separation,

t
is the permittivity of the medium. The permittivity of a vacuum, t 0 , is
8.85 x 10- 11 C 2 m- 1 J - 1 For common polar solvents, however, the permittivity values are considerably higher. For example, the permittivity is
7.25 X 10- 1 C 2 m - 1 r 1 for water, 2.9 X 10- 1 C1 m -
for acetonitrile,
and 22 X ro-to C 1 m-
for ammonia, giving relative permittivities of
82 e0 (H1 0). 33 to (CH 3CN), and 25 e0 (NH 3 ). Since the permittivity of ammonia is 25 times that of a vacuum. the attraction between ions dissolved in
ammonia, for example, is only 4"1. as great as in the absence of solvenL For
solvents with higher pennittivities the effect is even more pronounced.
Another way ot looking at this phenomenon is to consider the interaction
between the dipole moments of the polar solvent and the ions. Such solvation
will provide considerable energy to otrset the otherwise unfavorable energetics
of breaking up the crystal lattice (see Chapter 8).
94
4 lonclln 8 Mocloa. In lnorelc Chmlatry: I. tonic CoMpo,ucla
Occurrence of Ionic
Bonding
Simple ionic compounds form only between very active metallic elements and very
active noMlCtals.' Two important requisite$ are that the ionization energy to form
the cation, and the electron affinity to form the anion, must be energetically favorable.
This does not mean that these two reactions must be exothermic (an impossibilitysee Problem 4.13), but means, rather, that they must not cost too much energy. Thus
the requirements for ionic bonding are (I) the atoms of one element must be able to
lose one or two (rarely three) electrons without undue energy input and (2) the atoms
of the other clement must be able to accept one or two electrons (almost never three)
without undue energy input. This restricts ionic bonding to compounds between the
most active metals: Groups IA(I), IIA(2), part of IUA(3) and some lower oxidation
states of the transition metals (forming cations), and the most aaive nonmetals:
Groups VIIA(17). VIA(I6), 3 and nitrogen (forming
All ionization energies
are endothermic, but for the metals named above they are not prohibitively so. For
these elements, electron affinities are exothermic only for the halogens. but they are
not excessively endothermic for the chalcogens and nitrogen.
Structures of Crystal
Before discussing the energetics or lattice formation, it will be instructive to examine

some of the most common arrangements of ions in crystals.. Although only a Jew of
the many possible arrangements are discussed, they indicate some of the possibilities
available for the formation of lattices. We shall return to the subject or structure after
some basic principles have been developed.
The first four structures de$cribed below contain equal numbers or cations and
anions, that is, the I: I and 2:2 salts. Most simple ionic compounds with such formulations crystallize in one or these four structures. They dill'er principally in the
coordination number, that is, the number of counterions grouped about a given ion.
in these example$ four, six, and eight.
Lattlce5
The sodium chloride structure. Sodium chloride crystallizes in a face-centered

cubic structure (Fig.
To visualize the race-centered arrangement, consider
only the sodium ions or the chloride ions (this will require extensions of the sketch
or the lattice). Eight sodium ions form the corners of a cube and six more are
centered on the faces of the cube. The chloride ions ore similarly arranged, so that
the sodiwn chloride lattice consists or two interpenetrating race-centered cubic
lattices. The coordination number (C.N.) of both ions in the sodium chloride
lattice is 6, that is, there are six chloride ions about each sodium ion and six
sodium ions about each chloride ion.
Sodium chloride crystallizes in the cubic space group fmJm (see Table 3.7).
that is, it is face-centered, has a three-fold axis, and has two mirror planes of
different class. If there is one C 3 axis. however, three others must exist. and the
It is true tho! ionic compounds sllCh as [NH4 ) [B(C.H,).] arc known In which there are 110 extremely
aaive metals or nonmcu.ls. Ncvcrtbc:lcsr, the abo"< atatanent is for :Ill pnct.lcal purposes
and
we can consider ccmpouncls such as ammonium leuopheftytborale to r..ult from the particulAr covalent
bondina propenies cJ nit rep w boron.
Recall Crom tbc cliscussicn in Chapl<r 2: Roman num<nls are from the "Arncricon S)llcm" and Arabic
numero1s ore Crom 1be " 1- 18 S)'llem" cJ labdlnathe periodl< sable.
Sina: the lnnsition between icric bondi.,. ond covola\l bond!.,. is no1 a 11\arp one, iJ is tmpooaiblo
to define pm:Uely !he conditiom
which it wil occur. HOWCV<F, the ......,alizalion is helpful and
does not rule out tbc pouibility cJ un-.allonic bonds, lot example, between two m<1a1s: u' Au- . See
O..p<er 12.
2
Th loftlc len,.
95
(a)
(b)
Fig. 4.1 CI")'Stal structures or two I: I ionic compounds: (a) unil ced of sodium chloride.
cubic, space group Fm3m: (b) unit cell or cesium chloride, cubic, space group l'!n3m. (From
L:ldd. M . F. C.
wtd Bending in Solid
01tmlstry. Wiley. New York, 1979.
Reprodoo:d with permission.]
presence of two different mirror planes requires seven others. In fact, this compact symmetry label is enough to tell us that all elements of symmetry round in
an octahedron :.re present. Thus, the Schoenfties equivalent of Fm3m is o.
The sodium chloride structure is adopted by most of the alkali metal halides:
All of the lithium, sodium. potassium, and rubidium halides plus cesium fluoride.
It is also found in the oJtides of magnesium, calcium, strontium, barium, and
cadmium.
Tire cesium clrloride structure. Cesium chloride crystallizes in the cubic arrongement shown in Fig. 4.lb. The cesium or chloride ions occupy the eight
comers of the cube and the counterion oocupies lhe center of the cube. Again,
'llv: slnlclure d CsCt lhould not be rdCtml 10, inconcdly, u "body-cmrcted cubic". True bcdya:ntaed c:ubic la!tica ll:>.we tho:
JPCCics on the comcn and tho:
ol tho uril cell. as in tho:
alkali metals, roc cumpk.
s..,..
96
4 londl n Modo II In Inorganic Cho mlalr y 1 . Ionic Compound&
we must consider a Iauice composed either of the cesium ions or of the chloride
ions, both of which have simple cubic symmetry. The coordination number of
both ions in cesium chloride is 8; that is, there are eight anions about each cation
and eigl'lt cations about each anion. The space group is PmJm: The lattice is
primitive, but otherwise the symmetry elements are the same as in NaCI.
Among the alkali halides, the cesium chloride struct ure is found only in
CsCI, CsBr, and Csl at ordinary pressures, but all of the alkali halides except
the salts of lithium can be forced into the CsCI structure at higher pressures.
It is also adopted by the ammonium halides (except NH 4 F), TICI, TIBr, 11CN.
CsCN, CsSH, CsSeH, and CsNHl.
The zinc blende and wurtzite structures. Zinc sulfide crystallizes in two distinct lattices: hexagonal wurtzite (Fig. 4.2a) and cubic zinc blende (Fig.
We
shall not el8borate upon them now (see page 121), but simply note that in both
the coordination number is 4 for both cations and anions . The space groups are
and F43m. Can you Jell which is which?
..,
(b)
Fig. 4.2 Unit cells of two zinc sulfiide (2:2) $lrUctures: circles in order o( decreasing size
are S and Zn: (a) wurl2ile. hexqonal. space lfOUP P6)111C'. lb) zinc blende. cubic. space
aroup F43m. (From Ladd, M. F. C. Structuu tmd Bonding in Solid Statr
Wiley:
New Yen. 1979. Reproduced with permission.)
Tho I onic lon"
97
Fig. 4.3 Unit ceU of the
fluorite suucture; smaller

circle is Ca (not drawn to
scale): cubic. space group
Fmlm. [From Ladd,
M. F. C.
and
Bottdirtg ill Solid State
Cl..mlstry; Wiley: New
York. 1979. Reproduced

wilh permission.)
Many divalent metal oxides and sulfides such as BeO. ZnO, BeS, MnS, ZnS,
CdS. and HgS adopt the zinc blende or wurtzite structures, or occasionally both.
Other compounds with these structures include Agi, NH .. F, and SiC.
All the following structures have twice as many anions as cations (I :2 structures); thus the coordination number of the cation must be twice that of the
anion: 8:4, 6 :3,4:2, etc. The inverse structures are also known where the cations
outnumber the anions by two to one.
The fluorite structure. Calcium fluoride crystallizes in the fluorite structure,
cubic Fm3m (Fig. 4.3). The coordination numbers are 8 for the cation (eight
fluoride ions form a cube about ench calcium ion) and 4 for the anion (four
Ca 2 .. ions tetrahedrally arranged about each F Many difluorides and dioxides are found with the fluorite structure. Examples are the fluorides of Ca. Sr. Ba, Cd, Hg, and Pb, and the dioxides of Zr, Hf,
and some lanthanides and actinides. If the numbers and positions of the cations
and anions are reversed, one obtains the antifluorite structure which is adopted
by the oxides and the sulfides of Li. Na. K, and Rb.
Tire rutile structure. Titanium dioxide crystallizes in three crystal forms
at atmospheric pressure: anatase, brookite, and rutile (Fig.
Only the last
(tetragonal P4Jmnnr) will be considered here. The coordination numbers are 6
for the cation (six oxide ;mions arranged approximately octahedrqiJy about the
titanium ions) and 3 for the anion (three titanium ions trigonally about the oxide
ions). The rutile s tructure is also found in the dioxides of Cr. Mn, Ge, Ru. Rh,
Sn, Os, lr, Pt. and Pb.
P-crisloballte structure. Silicon dioxide crystallizes in several forms
(some of which are stabilized by foreign atoms). One is P-cristobalite (Fig. 4.4b).
which is related to zinc blende (Fig. 4.2b) having a silicon atom where every zinc
and sulfur atom is in zinc blende, and with oxygen atoms between the silicon
atoms.6 Other compounds adopting the P-cristobalite structure are BeF1 , Zn01 ,
SiS 2 at high pressures. and Be(OHh and Zn(OH)z, although the latter are distorted by hydrogen bonding. Another form of Si01 , tridymite, is related to the
The sJI'UClure al tkrislobalitc flu bcH dcUnnincol

rimes ov.,. the pua 60 ycon. 1>u1 aySI:II
disord<r flu led eo unc:eruJoty in the space poup uslpment (Hycle. B. G.:
S. 1-rDI'Iic
Crystal Strvcftltrs; Wiley: New Yort. 1989; P9 393-39$.
91
4 Bonding Mocleh in
1110fQOftlc
Chemistry: 1. Ionic Compo und a
(8)
(b)
Fig. 4.4 Crystal sruc:tures of 1wo more I :2 compounds; oxygen is lhe larger cird e in both:
(a) unit cell of rutile, Ti02 , tetragonal, space group P42 frmun; (b) unit cell of p..cristobalite,
SiO,. (From ladd, M. F. C. Structure and Bondi11g in Solid Stale Clremistry; Wiley:
New York, 1979. Reproduced wilh permission]
wurtzite structure in the same way that P-cristobalite is related to zinc blende.
The coordination numbers in P-cristobalite and tridymite are 4 for silicon and 2
for oxygen.
The calcire and aragonire strucwres. Almost all of the discussion in this
chapter is of compounds containing simple cations and anions. Nevertheless,
most of the principles developed here are applicable to crystals containing polyatomic cations or anions, though often the situation is more complicated. Examples of two Structures containing the carbonate ion,
are co/eire (Fig. 4.5a)
and aragonite (Fig. 4.5b). Both are calcium carbonate. In addition MgC03 ,
FeC03 , LiN0 3 , NaN03 , InB03 , and YB0 3 have the calcite structure (rhombohedral IUc). The coordination number of the metal ion is 6. Larger metal ions
adopt the aragonite struaure (orthorhombic Pcmn) with nine oxygen atoms
about the metal ion. Examples are, in addition to calcium carbollllte, SrC03 ,
KN03 , and LaB0 3
h lllce Ene r gy
99
(O)
Fig. 4.5 Crystal structures of two forms or

Cllrbont.te: (a) unit cell o( calcite,
rhombohedral space group Rlc: (b) unit cell cl
o"horhombic. space group Pcmn.
Circles in decrCliSing order or size are oxygen. calcium. t.nd carbon. (From Ladd. M. F. C
and Bonding in SoliJ
Wiley: New York. 1979. Reproduced with
permission.]
Lattice Ene rgy
The energy of the crystal lattice of an ionic c.ompound is the energy released when
ions come together from infinite separation to form a crystal:
+ XiSI
----+
MXr
{4.2)
It may be treated adequately by a simple electrostatic model. Although we shall

include nonelectrostatic energies. such as the repulsions of dosed shells.
more
sophisticated treatments include such factors as dispersion forces and zero-point
energy, simple electrostatics BIXOunts for abollt 90",4 of the bonding energies. The
theoretical treatment of the ionic lattice energy was initiated by Born and Lande,
and a simple equation for predicting lattice energies bears their names. The derivation ronows.
1 DD
4 l on tl l n11 Metlel o In lnorgenl c CheM i olrY l . le n ic Ce mpe 11ntlo
Fiv- 4.6 Energy curves for

an ion pe.ir.
'II
I
I
\..,
\
\ ,_
......._,
Consider the energy of an ion pair, M +, x-, separated by a distance r . The
electrostatic energy of attraction is obtained from Coulomb's law.7
zz-
Ec = 4xeor
(4.3)
Since one of the charges is negative, the energy is negative (with respect to the energy
at infinite separation) and becomes increasingly so as the interionic distance de
creases. Figure 4.6 shows the coulom bic energy of an ion pair (dotted line). Because it is common to express z and z- as multiples of the electronic charge,
e = 1.6 x w- 9 coulomb, we may wri te:
zz-e 2
Ec= - -4Ktor
(4.4)
Now in the crystal lattice there will be more interactions than the simple one
in a n ion pair. In the sodium chlo ride la uice, for example, there are attractions to
the six nearest neighbors of opposite cha rge, repulsions by the twelve next nea rest
neighbors of like cha rge, etc. The summation of all of these geometrical interactions
is known as the M ade/ung constant, A . The energy of a pair of ions in the crystal is
then:
Azz-e2
Ec=--:, - - -
4n&or
(4.5)
The evaluation of the Maddung consta nt for a particular lattice is straightforward

Consider the sodium ion() at the center of the cube in Fig. 4.7. Its nearest neighbors
a re the six face-<:entered chloride ions (e ). each at a characteristic distance determined by the size of the ions involved. The next nearest neighbors are the twelve
sodium ions (0) centered on the edges of that unit cell (c[ Fig. 4.1a inverted). The
distance of these repelling ions can be related to the firs t distance by simple geometry,
as can the d istance of eight chloride ions in the next shell (those at the corners of
the cube). If this process is followed until every ion in the crystal is included, the
Note !bat these .,.. iortlc dtarfiQ and no1 nuclear c:llaraes for which Z is also uscc1.
latllce Energy
101
Fig. 4.7 An extended lattice of sodium chloride. Starting with the sodium ion marked .
there are six nearest neighbors (e). twelve next nearest neighbors (0), eight next, next
nearest neighbors (darkly shaded), and so on.
Ma4elung constant, A, may be obtained from the summation of aU interactions. The

first three terms for the interactions described above are
12
8
A=6 - - + - ..
J2
.jj
(4.6)
Fortunately, the Madelung constant may be obtained mathematically from a

converging series, and there are computer programs that converge rapidly. However,
we need not delve into these procedures, but may simply employ the values obtained
by other workers (Table 4.1). The value of the Madelung constant is determined
Table 4.1
Madelung conslanh
of some common
crystal lattices
102
4 lorallllne Mollllela In l noreenlc Chemhtry: t . lenic Com,ou,uh
only by the geometry of the lattice and is independent of ionic radius and charge.
Unfortunately, previous workers have orten incorporated ionic charge into the value
which they used for the Madelung constant. The practice appears to have arisen
from a desire to consider the energy of a
such as MX 2 :
(4.7)
Zi
z-
where A = 2A and
is the highest common factor of
and
(I for NaCI,
CaF 2 , and Al 20l; 2 for MgO, T i0 2 , and Re0 1 ;
We could ignore this confusing
practice and use t he geometric Madelung consta nt, A, only, except that values reported in the literature are a lmost invariably given in terms of Eq. 4. 7. Values for
both A and A are given in Table 4. 1, and the reader may readily confirm that use
of either Eq. 4.5 or 4.7 yields identical results.
Returning to Eq. 4.5 we see that unless there is a repulsion energy to balance
the anractive coulombic energy, no stable lattice can result. The attractive energy becomes infinite at infinitesimally small distances. Ions are, of course, not point charges
but consist of electron clouds which repel each other at very close distances. This
repulsion is shown by the dashed line in Fig, 4.6. It is negligible at large dist ances
but increases very rapidly as the ions approach each other closely.
Born suggested that this repulsive energy could be expressed by
(4.3)
where 8 is 01 const:JnL Experimenl311y, infonnation on the Born exponent, n. may be

from compressibility data, bec:luse the laner measure the resistance which
the ions exhibit when forced to approach each other more closdy. The total energy
for a mole of the crystal lattice containing an Avogadro's number, N. of units is
(4.9)
The total lanicc energy is shown by the solid line in Fig. 4.6. Th.: minimum in the
curve. corrcspondinll to the equilibrium situation. may be found readily:
(4.10}
Physically this corresponds to equating the force of electrostatic auraction with the
repulsive forces between the ions. It is now possible to evaluate the constant 8 and
remove it from Eq. 4.9. Since we have liJced the energy at the minimum, we shall use
Fer btb<r clisC1wion o/ 1.... problem ol cld'ring Maddurc ccnstants, sec Quane. D. J. 0-. Jvc.
1970. n.l96.
Lettice hergy
103
U0 and r0 to represent this energy and the equilibrium distance. From Eq. 4. 10:
Table4.2
ValuHoltllo . .m
exponeftf,n
lon conneuration
He
Ne
Ar, eu
Kr, Aa
Xe. Au
(4.1 I)
5
1
(4.12)
10
(4.13)
12
This is the Born- Landi: equation for the lattice energy or an ionic compound. As we
shall see, it is quite successful in predicting accurate values, although it omits cenain
energy factors to be discussed below. It requires only a knowledge of the crystal
stnJcture (in order to choose the correct value for A) and the interionic distance, ro.
both of which are readily available from X-ray diffraction studies.
The Born exponent depends upon the type of ion involved, with larger ions
having relatively higher electron densities and hence larger values of n. For most
calcui:ltions the generalized values suggested by Pauling (sec Table 4,:!) are sufficiently accurate for ions with the electron configurations shown.
The use oC Eq. 4.13 to predict t he lattice energy or an ionic compound may be
iUustrated as follows. For sodium chloride the various factors are
A= 1.747S6(Table4.1)
= 6.022 x tou ion pairs mol - '. Avogadro's number
z = +I. the charge of the Na
z- =
e = 1.60218
It=
ion
-I. the charge of the Cl - ion

x 10-
19
C. the charge on the electron (Appendix B)
3. 14159
o :: 8.85411!8
w-: c: r
m - I (A ppcndix B)
r0 = 2.814 x 10- 0 m. the experimental value. If this is not available. it may

be estimated as 2.83 x 10- 10 m. the sum of radii or Na and a(T able 4.4).
n = 8. the average of the values for Na and
a - (Table
Performing the arithmetic. we obtain U0 .. - 155 kJ mol - 1, which may be compared

with the best experimental value (Table 4,3) oC - 110 kJ mol - 1 We may feel confident using values predicted by the
equation where we have no experi
mental values.
As long as we do not neglect to understand each oC the factors in the Bom-landi:
equation (4. I 3), we can simplify the calculations. It should be
that the only
variables in the Bom-Landi: equation are the charges on the ions, the internuclear
distance, the Madelung constant. and the value oC n. Equation 4. 13 may thus be
simplified with no loss of accuracy by &rouping the constants to give:
104
4 Bonding Modeh Jn tnorsnnlc Che mlatry: t .. Ionic Compounch
U0 = 1.39 x 105 kJ mol- 1 pm
1)
r(-zz-A)(
0
I- ;
(4.14)
Note that the internuclear distance should have the units of picometers, as given in
Table 4.4. If working with angstrom units and kcal mol- 1 , the value of the grouped
constants is 332 kcal mol- 1 A.
Equation 4.13 accounts for about 98% of the total energy of the lattice. For
more precise work several other functions have been suggested to replace the one
given above for the repulsion energy. In addition. there are three other energy terms
which affect the result by a dozen or so kJ mol - 1: van der Waals or London forces
(see Chapter 8), zero-point energy, and correction for heat capacity. The latter arises
because we are usually interested in applying the results to calculations at temperatures higher than absolute zero, in which case we must add a quantity:
6 =
(Co(MX) - cOJM.I - Co(X -))dT
(4.15)
c.
where the
terms are the heat capacities of the species involved. 9
The best calculated values, taking into account these factors, increase the accuracy somewhat: U0 = - 778, overestimating the experimental value by slightly less
than 1%. Unless one is interested in extreme accuracy, Eq. 4. 13 is quite adequate.
The Born-Haber
Cycle
Hess's law states that the enthalpy of a reaction is the same whether the reaction
takes place in one or several steps; it is a necessary consequence of the first law of
thermodynamics concerning the conservation of energy. If this were not true, one
could "manufacture" energy by an appropriate cyclic process. Born and Haber10
applied Hess's law to the enthalpy of formation of an ionic solid. For the formation
of an ionic crystal from the elements, the Born-Haber cycle may most simply be
depicted as
M(fl
-----'"=H'-",.,__ __
+
XIIII
l>Jt,...
iX 2(11
i>HoA
x;;.
tv
MX1, 1
It is necessary that
t.H1 t.H,... + l1H,>< + f>Hu!. + t.He, + U0
(4.16)
The terms 6H,.. and 6H,71 are the enthalpies of atomization of the metal and the
nonmetal, respectively. For gaseo us diatomic nonmetals, t.H,. is the enthalpy of dissociation (bond energy plus RT) of the diatomic molecule. For metals which vaporize
to form monatomic gases, 6H11 is identical to the enthalpy of sublimation. If sublimation occurs to a diatomic molecule, M 2 , then the dissociation enthalpy of the
reaction must also be included:
It is commonly assumed thai the independent cations and anions will behave as ;deal m<N.tanic SIISC$
willt hear capacilies (al con5Janl volume) d iR.
oo Born. M.
Dtut. Physik. Cts. ttl,, 11. 13; Haber. F.: Ibid. 1919,:11. 7SO.
9
lelllce Energy
M 2 ----+ 2M
105
(4.17)
Values for the ionization energy, IE, and the electron affinity, EA, may be obtained from Ta bles 2.3 and 2.5. Bond dissociation energies for many molecules arc
given in Appendix E. A useful source of many data of usc to the inorganic chemist
has been written by Ball and Norbtlry. 11
Use5 of Born-Habet'Type Calculation$
The enthalpy of formation of an ionic compound can be calculated with an accuracy

of a few percent by means of the
equation (Eq . 4. 13) and the BomHabcr cycle. Consider NaO, for example. We have seen that by using 1he predicted internuclear distance of 283 pm (or the experimental value of 281.4 pm), the
Madelung constant of 1.748, the Born exponent, n, and various constants, a value
of - 1SS lcJ mol- 1 could be calculated for the lattice energy. The heat capacity
correction is 2 1 kJ mol- 1 , which yields
= -757 kJ mol - 1 The Bom-Haber
summation is then
I!J.H1E
I!J.HEA
= -757 kJ mol - 1
= +496 kJ mol I
= -349 kJ mol -
+ 12 1 kJ mol - 1
I!J.HAN = + 108 kJ mol- t
-38 llcJ mol- 1
llHAc1
This can be compared with an experimental value for the enlhnlpy of formation,
tili}98 = -411 kJ mol - 1
Separation of the energy terms in the Born-Haber cycle gives us some insight
into their relative importance in chemical bonding. For example, the I!J.HA tcnns are
always positive, but are usually of relatively small size compared with the other terms
and do not vary greatly from compound to compound.ll The ionization energies
are always greatly endothermic. Electron affinities for the halogens are exothermic,
but for the chalcogcns they are endothermic as a result of forcing the second electron into the nega tively charged x- ion. In either case, the summa tion or ionization
energy and electron affinity Is always endot hermic, and it is only the overwhelming
exotherrnicity of the attraction of the ions fo r each other that makes ionic compounds
stable with respect to dissociation into the elements. At room temperature this energy
a ppears as the lattice energy. It s hould not be -supposed, however, tha t at temperatures above the boiling point of the compound (1413
for NaCI, for example) no
reaction would occur between an active metal and nonmetal Even in the gas phase
there will be electrostatic stabilization of the ions through the formation of ion pairs,
M +x- . The latter should be added to the Born-Habcr cycle, and to clarify the
nature of the energy relationships, it is best to draw it in more
form as in
Fig. 4.8. In such a diagram the individual cnthalpies can be portrayed and related
13
to the original enthalpy of the starting materials.
oc
BaU. M. Norbury, A. H. Plo1fkol Dora fot' /norgork CIIDfllsJs; LoniJTI'ln: London. 1974.
u This SJatemcnt is 11riclly Irue only for the halol!<ns. The dissociation encraic3 of 0 1 and N2 an: considerably Jaraer.
I I
n For a discuosicn ri this poinl as well as several othen concemina Bom- Haber-lype cycles. see
G. Jr. J. Clomt. Ethic. 1968,4$,420.
106
41ontl l ng Models In Inorg anic Chemhlry : 1.lnlc Camounllla
800
640
S60
480
EA - 348.S
400
320
""' s
N0 , +iCiu0 1 li.IIAa 120.9

11
80
t.HAHo =
108.4
u...,,..,- 4SO.l
u. -787.o
No111 +iCr, 011
-80
-;60
u....,.. - 336.1
I
Fig. 4.8 Born- H:rber tli3gram showinG
of various terms for sodium
chloride. (Adapted from HaiGhL G. P, Jr. J . Chtm. Juc. 1968. <IS. 420-422. Reproduced
with permission.]
M05t of the enthalpies associated with steps in the cycle can be estimated, to a
greater or less accuracy, by experimental methods. The lattioe energy, however. is
almost always obtained theoretically rather than from experimental measurc:menl It
might be supPosed that the "enthalpy of dissociation" of a lattice could be measured
in the same way as the enthalpy of atomiz:uion cl the metal and nonmetal, that is.
by heating the crystal a nd determininy how much energy Is necessary to dissociate it
into ions. Unfortunately, lhis is experimentally very difficult. When a cryst:tl sublif'lli.'S
(6Hs), the result is not isolated gaseous ions but ion pairs und other clusters. For
this reason it is necessary to usc: Eq. 4.13 or some more accu rate version of it. We
can t hen use the Born-Haber cycle to check the accuracy of our predictions if we can
obtain accurate data on every other step in the cycle. Values compu ted from the
Born-Haber cycle are compared with those predicted by Eq. 4. 13 and its modifications in Table 4.3.
Onoe we have convinced
that we are justified in using theoretical values
for U0 , we can use the cycle to help obtain infontllltion on nny other step in the cycle
which is experimentally difficult to measure:. For many yenrs eleclron affinities were
obtained alm05t exdusively by this method since accurate esti!Tllltes were difficult to
obtain by direct experiment
FltlliUy, it is possible to predict the heat d fonnation d a new and previously
unknown compound Reasonably good estimates of enthalpies of atomization. ionization energies, and electron affinities are now available for most elements. It is
Lallie notgy
1 07
Table4.3
E>cperimental and cakulotecl
lottlce -ales ( -U0 ) of
al<oli halicles (kJ mol- 1 )
Simple moclel
Sail
LiF
LiCI
Li:BtLil
NaF
NaCI
NaBr
NaJ
KF
KO
KBr
KI
RbF
RbCI
RbBr
Rbi
CsF
CsCI
CsBr
Cs1
(tq.4.13)
1034
1008
9S21
803.7
792.9
713.0
902.().
755.2
m.8
718.8
739.3
752.9
713.4
8113
781.2
718.4
914.2
108A
812.1
701.2
"671.1
632.2
780.3
682.4
654.0
616.7
743.9
629.7
612.5
5845
appro>dmatlon
lOll
845.2
7979
719.7
915.0
840.1
770.3
728.4
680.7
Kapuotlnsldl
"'lesl valu.....
766.1
663.2
692.0
797.5
676.5
659.8
623.0
813.4
708.8
761.1
661 .5
636.4
602.5
723.0
622.6
599.6
568.2
619.S
640.2
7n.8
686.2
659.0
622.2
747.7
652.3
632.2
601.2
884.9
673.6
788.7
680.7
6749
613.8
760.2
661.9
626.3
589.9
713.0
625.1
602.1
563.6
Cok:ulated usin& a modified Born cquaJion wilh corrcetio111 for polari%ation eft'ccu, I<jllllslon
belween nearesJ and nell no:aJat n<iaJ>bon, aud zero-point enerv (Cubia:iolli, D. J. Ocm.
Ploy 1959, Jl, 1646-1651; lbiJ.. 1961, J4,
See Eq. 4.20.
then nceessary to make some good guesses as to the most probable lattice structure.
including intemudear distances and geometry. The internuclear distance can be estimated with the aid of tables of ionic radii. Sometimes it is also possible to predict
the geometry (in order to know the correct Madelung constant) from a knowledge
of these radii (sec next section). In such a case it is possible to predict the lattice
energy and the enthalpy of formation (the latter almost as accurately as it could be
measured if the compound were available). Examples of calculations on hypotheticnl
compounds are given below. and a final example utilizing several methods associated
wilh ionic compounds is given on page 127.
Consideration of the terms in a Born-Haber cycle helps rationalize the existence
of certain compounds and the nonexistence of others. For example, consider the hypothetical sodium dichloride, Na1 , 2CI-. Bceause of the +2 charge on the sodium
ion. we might expect the lattice energy to be considerably larger than that of NaCI.
adding to the stability of the Compound But if all the terms are evaluated, it is found
that the increased energy necessary to ionize sodium to Nn 2 more than that which
is returned by the increased lattice energy. We can make a very rough calculation
nssuming that the internuclear distance in Na0 2 is the same as in NaCI 14 and that
We
adequate.
see thai t!Us ovo:reslirnot<J the distance, but for tho praenr approximation it should be
'
108
4 lon4lng Mo4eh In lnor1 onic Chemilfy; 1 . llc Co pountfa
it would crystallize in the fluorite structure with a Madelung constant of A = 2.52.

The lattice energy is then U 0 = - 2180 kJ mol - 1 The summation of Bom-Haber
terms is
U0
= - 2180
= + 108
ll.HaE, = + 496
ll.H1, = +4562
26H ;,._ = -698
/j}fANo
/j}fAco
= +242
ll.H1 = +2530 lcJ mol-
Although the estimation of U 0 by our crude approximation may be otr by 10-20"/o,

it cannot be in error by over I 00"/o, or 2500 kJ mol- 1 Hence we can see why Naa 2
docs not exist The extra stabilization of the lattice is insufficieru ro ccmpefiSQte for
the very large second Ionization energy.

A slightly different problem arises when we consider tbe lower oxidation states
of metals. We know that CaF 2 is stable. Why not CaF as well? Assuming that
CaF would crystallize in t.be same geometry as KF and that the internuclear distance would be about the same, we can calculate a lattice energy lOr CaF, U0 =
-1951cl mol - 1 The terms in the Bom-Haber cycle are
U0
= -795
= +178
fl.HIE
+590
+ 79
fl.HEA
/j}f,._ F
= -328
fl.H1 = -276 kJ mol - 1
An enthalpy of formation of - 276 kJ mol- 1 , though not large, is perfectly acceptable because i t is about the same as that of Lil, for example. Why then does
CaF not exist? Because if one were able to prepare it, it would spontaneously disproportionate into CaF1 and Ca exothermically. 1 '
2Co F --+
2fl.H1 = -550
(4.18)
t.H, = -670 kJ mol - 1
An examination of the ionic compounds of the main group elements would show
that all of the ions present have electronic configurations that are isoelectronic with
noble gases; hence the supposed "stability of noble gas configurations". But what
type of stability? It is true tha t the halogens are from 295 to 350 lcJ mol- 1 lower
in energy as halide ions than as free atoms. But the fonnation of the 0 2 -, S2 -,
N 3 -, Li+, Na+, Mg 2 +, a nd Cal+ ions is endothermic by 250 to 2200 lcJ mol-. Even
though these ions possess noble gas configurations, they represent higher energy states
than the free atoms. The "stability" of noble gas configurations is mea.ningless unless
one considers the stabilization of the ionic latt.ice. For the main group clements tbe
chemical reacaion will be determined by lhe free mngy, li.G, not lhe enthalpy, li.H.
How.veF, iD aloe Pft*nl IQdion aloe
tcnn, AS, is op to be compal'llivdy smoll aod lincc
li.G = llH - T li.S, 1hc rree CnetJY will be dominated by the eruhalpy at mudcnte !mlperuures.
" The dinction
Lettice hIY
109
noble gas configuration is that which maximizes the gain from high charges (and
large lattice energies) while holding the cost (in tenns of ionization potential-electron
affinity energies) as low as possible. This is shown graphically in Fig. 4.9. Although
the second ionization energy for a metal is always larger than the first, and the third
larger than the second, the increase is moderate except when a noble gas configuration is broken. Then the ionization energy increases markedly because the electron
is being removed from the n - I shell. Below this limit the lattice energy increases
faster with oxidation state than does the ionization energy, so that the most stable
oxidation state is the one that maximizes the charge without breaking the noble gas
configuration. This is why aluminum always exists as Al 3 + when in ionic crystals
despite the fact that it costs 5 140 kJ mol - 1 to remove three electrons from the atom!
For transition metals, all electrons lost on ionization are either ns or (n - l}d
electrons which, as we have seen, are very similar in energy. Hence there are no
abrupt increases in ionization energy, only the more gradual change accumulating
from loss of electrons to fonn higher 'Z:' +, and these will be compensated by higher
lattice energies. Consider, for example, CuO and Cu01 . We may calculate (d. Prob-
or
AJ
=- 16,000
'oe
e
0
:;l
12.000
3,000!
2.000
8,000
"
.!!
..
;;
1.000
2 4,000
.l!
OMocbtlon IIIlO
AIX4
8,000
!.000
...
.s
'll0
.....,li
.."f
...
1i
, ,,00
6,000
4 ,000
1,000
.rl!
.8
!
soo
21!00
"
.2
..
.ll
..
-soo "'
'o
"'" -21!00
+I
+2
+3
Oxi<laclon IIIlO
+4
or
or
ore a/wuys lttS$ stnblt in
Fig. 4.9 Energies of free

cations and ionic
compounds as a function
the oxidat.i on Slate
the cation. Top: Unes
represent the ionization
energy
to form
the+ I, +2. + 3, and
+ 4 ations of sodium.
magnesium. and aluminum.
Note that although the
ionization energy increases
most sharply when a noble
gas configuration is
isolated cations
ltf11htr uxiJtttion stult!S.

Bottom: lines represent the
sum or ioniz<uion energy
and ionic bonding energy
for hypothetical molecules
MX. MX., MXl, and MX4
in which the interatomic
distance, r0 , has been
set at 200 pm.
Note thai the most stable
compounds (identified by
arrows) an: NaX. MgX,,
and AIX 1 . (All of these
molecules will be stabili.zed
additionally to a srnaU
extent by the etec:tron
affinity or X.)
110
lon llllfttl Molllleh ln tnorgonlc Chemialryt l. lenic CoMpeuntllla
lem 4.25) the enthalpies of formation as foUows (lcJ
Term
CuCl
+338
+746
+ 121
- 349
-973
-117
+338
+746
+1958
+242
- 698
-2772
- 186
The enthalpy of atomization o( copper does not differ at a ll for the two compounds,
and the atomization of chlorine adds only a small difference for the second mole or
chlorine. The major energy cost for CuCJ1 is rhe second ionization energy ol copper
which is compensared by the electron affiniry ro form the second chloride ion and
especially the lattice energy. Since rhe electron ionized to form Cu1+ is a d electron
and does nor brealc a noble gas structure. IE1 is not excessive, and both CuCI and
CuCI2 are srable compounds.
Some Simplifications
and " Rules of
Thumb"
In the same way rhat Fig. 4.9 was sketched with ..average" values 10 illusrrate rhe
stabiliry ol compounds wilh noble gas configurations, we can simplify Eq. 4.14 further
by inserting some
values. II must be clearly understood that this is merefy
clearing away some o( rhe numerical shrubbery 10 lay out rhe picture ol rhe chemical
forest in clearer detail Let us assume rhat we are studying compounds M X- wirh
an imemuclear disrance ol about 200 pm. Of course.
I. To be as general as possible. lefs use an average value of A .. 2, which is not roo inaccurare
for presenr purposes (about 20% error) for NaO, Csa, CaF:. T.0 1 , and bolh ZnS
structures. Equation 4.14 reduces to
z "" -z- ..
U0
-1400kJ mot-
-330kcal mot -
- 14eV
(4.19)
This approximation is somewhat high for most compounds chiefly because an internuclear distance of 200 pm is too small for most compounds. But it has rhe useful
asset ol requiring that only the coefficients of Eq. 4.14 be remembered. Furthermore.
it allows some simple predictions to be made without involving the derailed calculation of the above examples. For example, can we make o .. rule of rhumb.. to predict
when a compound M+x- will be readily oxidized to Mu2x-? Using Eq. 4.14,
we predict that the lattice energy will double. or increase by one to one-and-a-half
MJ mot-, upon conversion to MX 1 . By far the major energy that has 10 be paid
to accomplish this change is IE1 of the meral While a thorough examination or all
of the energy terms is necessary for a careful analysis of the situation, we are led to
believe that if the additional cost ol ionizarion is less rhan about 1.3- 1.5 MJ mol- 1
(13- IS eV) for rhe higher oxidation s tate, it may well be stable, too. In the case of
copper, given above, we have
IE 1
= 0.75 MJ mot-
la 20 MJ mol- 1
IEJ- 3.5 MJ mol - 1
Our rule ol thumb follows the more carefUl calcularions above and predicts that both
Ol{I) and 01{11) compounds will be stable and, furthermOfe, it also works where
data are not available for a more careful analysis: Cu(III) compounds are predicted
to be unstable or marginaDy stable (Chapter 14).
Lettice Energy
111
On the other hand. if the succeeding ionization energies are too near each other,
as
was the case ror IE, and IE1 of calcium above:

IE, =0.6MJmol- 1
IE1 = 1.1 MJmol - 1
IE3 - 4.9MJmor-
then the lower oxidation state (Ca) is unstable because it is too readily oxidized to
Cal+. Of course, Ca1 is unavailable because it is too prohibitively expensive.
Ahrens, 16 who was the first to point out this rule of thumb, contrasted the behavior of titanium:
IE1 = 0.66 MJ mor-
IE1
,.
1.3 MJ mol-
IE3 = 26 MJ mol-'
IE4
4.2 MJ mol -
with that of zirconium:
IE,= 0.66 MJ mol- 1
re., ... 1.3 MJ mol-
IE3 = 22 MJ mol- 1
IE. - 3.3 MJ mol - 1
The differences between the successive oxidation states for titanium are just sufficient
to allow marginally stable 11(1) and Ti(lll) oxidation states in addition to Tr(IV). The
corresponding lower oxidat.ion states are uncommon for zirconium whose chemistry is
dominated by Zr(IV).
or intermediate accuracy between the rough rule or thumb given above and the
precise Born-tan& equation is a suuestion made by Kapustinskii. 17 He noted that
the Madelung constant. the internuclear distance. and the empirical IOnnula or a
compound ace all interrelated. ' 8 He has suggested that in the absence or knowledge
or crystal structure (and hence or the appropriate Maddung constant) a reasonable
estimation of the lattice energy can be obtained from the equation:
Uo
l20,200vZzro
(I -34.5)
(kJ mol- ' )
(4.20)
ro
where v is the number of ions per

or the compound and r 0 is estimated as
the sum or the ionic radii (Table 4.4), r + + r _ (pm). For the sodium chloride example
given previously, v "" 2 and r 0 = 28 1 pm, yielding a lattice energy of -750 kJ mol" 1,
or about 98% or the experimental value, comparing favorably with that obtained
from Eq. 4. 13. Of
the usefulness or Eq. 4.20 lies not in its prediction of the
Ahrens, L. H. G<Odlim. Co.<nU>dlim. AciD 1953, J. I . Ahrens v.llues, 8- IOeV. seem low in ohe liahl o(
subseq...,, experience. A cardiJ! analysis hauuaaestod that dll'len:nces o( 13- t5 ev (1 .3-I.S MJ mol" ' )
between successive Ionization
letod to multiple, stable oxiclation 1tates (Pone:field, w. w.
Clolmislry: A Ur.ijkJ Approccll; Addioon-Wesley. Rudina, MA, 1984; pP 4 16-420).
11
Kapuslloukii. A F. Z.
Clofflt.
t933, 811, 257: Zll. Fit. Khim. 1943, J, 59; (211<211. Rao.
Clrtm. Soc. 1956. 10. 283.

11
This (dloWs from the r.a 1'*. zjvm :t cetUin numba' of ionJ o( ccrtoio .U.S. the numba' o( w:1y1 o(
plltlcinslbem elllcielllly is sc.qdy limilod. Simple cases of Ita arc discuDod in lloc sectio.. mtiJiod
"EIIicimcy o( PacltiJW and Crystal
and "Rodiut Ratio". For more thotoup discuuion.s o(
Kapusainstii.. ....t. see Waddq10n, T. C AU.I- g. CNm. RIMikidttrtL 1959. I. IS7;
W. E.
11/l<da, 2nd ed.; Catobriola UM\'Cf>ity.
pP 76- 79.
11 2
4 lon .. inl Mo .. e lln Inorganic Chentl ltry: 1. lonlc Compou ..
lattice energy of sodium chloride. which is well known and provides a check on its
accuracy, but in giving reasonably accurate estimates for compounds that are not
wdl known (see Problem
In summary, in addition to allowing simple calculations of the energetics of
ionic compounds, the Bom- Haber cycle provides insight into the energetic factors
operating. Furthermore, it is an excellent example of the application of thermodynamic methods to inorganic chemistry a nd serves as a model for other, similar
calculations not only for solids, but also for reactions in solutio n and in the gas phase.
Size Effeds
Ionic Radii
The determination of the sizes of ions has been a fundamental problem in inorganic
chemistry for many years. Many indirect methods have been suggested for apportioning the internuclear distance between two ions, relatively easy to obtain, into
cationic and anionic radii. Although these have been ingenious and provide insight
into atomic properties, they are no longer necessary.
When an X-ray crystallographer determines the s tructure of a compound such as
Naa (Fig. 4.la). usually only the spacing of ions is determined, because the repeated
spacings of the atoms diffract the X rays as the grooves on a phonograph record
diffract visible light. However, if very careful measurements are made, accurate maps
of electron dmsity can be constructed since, after aR it is the electrons of the in-
Fig. 4.10 Electron density conlours in sodium chloride. Numbers indicate the electron
density (eleccrons A-- 10- 6 electrons pm - 3) along each coruour line. The "boundaryft or
each ion is defilled as the minimum in electron density between the ions. The intemuc:lear
distance is 281 pm
2.81 A). (Modified from Schoknecht, G. z.
1951, 12A,
983. Reproduced with permission.]
Size Effects
113
dividual atoms tha t scatter the X rays. The result is Fig. 4.10. One may now apport.ion the interatomic distance in NaCI, 281 pm, using the minimum in elect.ron density
as the operational definition of "where one ion stops and the other starts".
Although not many simple ionic compounds have been studied with the requisite
aocuracy to provide data on ionic radii, there are enough to provide a basis for
a complete set of ionic radii Such a set has been provided in the crystal radii of
Shannon and Prewitt 19 Values of these radii are given in T able 4.4.
Factors Affe cting

the Radii of Ions
A comparison of the values given in T able 4.4 allows one to rnalce some conclusions
regarding the various factors that affect ionic size. We' have already seen that progressing to t he right in a periodic series should cause a decrease in size. lf the ionic
charge remains constant, as in the + 3 lanthanide cations, t.he decrease is smooth
and moderate. Progressing across the main group metals, however, the ionic charge
is increasing as well, which causes a precipitous drop in cationic radii: Na ( 116
Mgz. (86 prn). AJH (67.5
In the same way, for a given metal, increasing oxidation state causes a shrinkage in size, not only because the ion becomes smaller as it
loses electron density, but also because the increasing cationic charge pulls the anions
in closer. This change can be illust.r ated by comparing the bond lengths in the complex anions FeCI! - and FeCl;. The Fe(Ul}- CI bond length is 11 pm shorter than
the Fe(II)-a bond length.2o
For transition metals the multiplicity of the spin state affects the way in which
the anions can approach the cation; this alters the effective radius. Although this is
an important factor in determining cat ionic radii, it is beyond the scope of the present
chap1er and wiD be deferred to Chapter 11.
For both cations and anions the crystal radius inaeases with tlte increase in coordination number. As the coordination number increases, the repulsions among the
coordinating counterions become greater and cause them to Mback off" a bit. Alternatively, one can view a lower coordination number as aOowing the counter-ions to
compress the oentral ion and reduoe its crystal radius.
As we shall see over and over again, the simple picture or biDiard-ball-like ions
of invariant radius is easy to describe but generally unrealistic. The fluorides and
oxides come closest to this picture, and so the values in Table 4.4 work best with
them. Larger, softer anions in general will present more problems. Little work has
been done in this area, but Shannon11 hus presented a ta ble, analogous to Table 4.4,
for sulfides.
Radii of Polyatomic
Ions
The sizes of polyatomic ions such as NHt and

are or interest for the understanding of the properties or ionic compou nds such as (NH4 hS0 4 , but the experimental difficulties attending their determination exceed those of simple ions. In addition,
the problem of constancy of size from one compound to the next-always a problem
Prcwiu, C T. Aau CtyJt4/logt. 1969. B1J, 925; Sronnoa, R. D. ibiL 1976. AJl, 7SI. M<t
inorganic boolc.s in the pas1. icdudit11 the ftrst edition oltbe pres<nt on<,
sj\'CII some set ol
"lr.lditk>nal'" iooic: radii t.acd on indirea cstimatq. The Slwlnon and Prewin aynol rG<III si..., in
Table4.4an: abcul 14 pm Joracr rorca1ionl &ad 14 pmaM&IIct ror anioMthon thc best act ohtadiliooal
10 Shannoa, R.;
ndii.
lauba', J. W;, Ibm, J. A. l 110tf1. 0wm. 1975, 14. 34&.
"ShaMon. R. 0 . In StiUOwt Olld Bon<l<tvt 111
O' Keefe. M.; Navrolslty. A., Eds.: A.cademic::
10
New Yen. 1911, VoL
16.
114
4 . lonllll ng Mo.t als In Inorganic Chmlatryr t. loftlc Co,.,pounllll a
Talole 4.A
.,. ............
lffective ionic rodii of
..........
Coordlnot!Oft
..........
Coanliftatj...,
Jon
),,;l..
Agl+
6
2
4
4SQ
6
7
8
4 SQ
6
4 SQ
6
4
Ag'
At
AJ'+
Am'
1
Am
Am..
;.rAs'
As'
All+
Au'
Au,.
Au'
Ba>+
6
7
8
9
6
8
6
8
6
6
4
6
6
6
4 SQ
6
6
3
4
6
6
7
8
9
10
II
12
3
4
6
Be
1
Bi3 +
...t: .
a>+
I
81?"'
'
6
8
6 --
ptll
Jon
126
81
114
116
123
129
136
142
93
108
81
Bk..
Br'sr'
or'
7
Br
c-
eaH
89
S3
62
67.5
135
Cd2
140
14S
lli.S
123
99
109
21()" ce
72
47.5
60
76
lSI
82
ee
99
71
IS
25
41
149
IS2
ISIS
161
166
171
17S
30
41
S9
110
117
131
90
110
cf'
aa'
a'
Cm'
em
ca
co .
8
6
4 SQ
3 py
4
6
3
4
6
6
7
8
9
tO
12
4
6
7
8
12
6
7
8
9
tO
12
6
8
10
12
6
6
8
6
3 py
4
6
6
6
8
4 HS 0
6 1..S'"
HS
8
6LS
HS
.........,.
Coonlinatien
pm
97
107
182
73
4S
39
53
6
29
30
114
120
126
132
Jon
co
(Y+
cr'
er..
cr'
Cr6
cs
4
6 HS
6LS
HS
6
4
6
4
6
8
4
6
6
8
137
148
10
92
II
101
cs109
eu-'
117
124
145
eu
liS
121
12l!.J
1)3.6
eu
139
Oy'
148
101
of"
I ll
121
oy
128
109
96. 1
106
Er'
167
26
22
41
1
Ill
Eu
99
109
72
6
6LS
2
6
7
8
6
7
8
9
6
7
8
9
6
7
8
9
81
Eu'
79
BB.S
104
' 68.S
7S
12
10
2
4
6
4
4SQ
F'-
10
6
7
8
9
2
pm
54
67
87
94
7S.S
ss
69
48.5
63
71
40
S8
t81
188
' 192
195
199
202
.348'"
60
74
91
71
71
79
87
68
4
121
127
133
IOS.2
I ll
116.7
122.3
103
108.5
114.4
120.2
131
134
139
144
149
108.7
liS
120.6
1!6 I
ll4.S
ContinuN
Size Uecta
Tobie 4.4 (ContinviHI}
......,.,.
Effe<live ioM rodii of
'" nlements"
Coorclinal;on
Jon
F'
Fe2
Fe'
3
4
6
6
4 HS
4 SQ HS
6LS
HS
8 HS
4 HS
Fe
Fe6
Fr 1
Ga'
Ge2
Ge4
H'
Hf..
Hg'
Hi
Ho
i'-
t
J'+
in1
22
ir,.
78
75
ir'+
K' K'
92
78.5
6
6
7
8
9
6
4
6
I
2
4
6
7
8
3
6
2
6
8
6
8
9
10
6
3PY
6
4
6
4
6
8
6
6
6
lr4
92
12.S La'+
39
194
61
69
76
107.8 Li'
114
li9.3
124.7 Lu'
87
53
67
-24
-4
72
85
90
97
Ill
133
83
110
Ji6
128
104. 1
llS.S
i2J.2
126
206
58
i09
S6
67
76
94
106
82
76.5
71
313'
151
152
160
165
169
173
178
117.2
124
130
4
6
7
8
106
63
72
HS
8 HS
4
3
116
117
119
69
5
Gd)+
ion
6LS
6
4
6
4
Coordination
number>
pm
pm
Mg'
9
iO
12
6
7
141
ISO
7J
90
106
100. 1
111 .7
117.2
71
80
5
Mn
6
8
4 HS
5 HS
6 LS
HS
7 HS
Mn.t.
5
6LS
Mn
Mn
Mn6
Mn7
Mo,.
Mo
Mo,.
HS
4
6
4
4
4
6
6
6
4
Coordination
ion
Mo6
N'-
N,.
N'
Na 1Na'
135.6 Nb,.
9
10
12
4
6
8
6
8
9
4
Nb
Nb'
Nd'
Nd 3
86
IOJ
80
89
81
97
104
110
72
115
Ni2
number
75
6
4
55
64
6
7
4
6
3
6
73
87
132
30
4.4
27
276'
113
114
116
126
132
138
153
86
6
7
8
9
12
6
6
8
4
6
7
8
8
9
6
8
9
12
82
93
62
78
83
88
4 SQ
5
Ne
Ni4
2
72
No
78.5 Np
Np'
53
Np<+
67
47
39.S Np,.
Np&
39
N
60
83
79
60
of-
6
6 LS
HS
6 LS
6
6
6
6
8
6
6
6
2
J
4
pm
143
149
112.3
124.9
130.3
141
69
63
77
83
70
74
62
124
124
liS
JOi
il2
89
86
85
J2i
122
i24
Cuntinued
116
4 Boncllne Motle la in lnOI'tJonlc Chemlahy: 1. Ionic Compountlc
Table 4A (Conti.....J)
.....,.......,,..
Coonlinotiooo
Effective ionic radii of
lon
numbe,-
--6 -
OH'"
8 '
2
3
4
6
6
pm
126'
128
Jl8
120
121
123
77
ton
Coordinofion
,_.,.,..
Pt
.6
pf+
Pt4 +
PtS+
68.S
66.S
4 SQ
. . v'6'
94
6
6
6
sffi
76.S
71
88
-40
'
.J
,,...
. . . S4 I
7 , "
. )36
141
'lh 146
-?- .
Sml+
110
It"'
8 ""
I 1
8
Pus.
131:9.
Coordinaticm.
"" ......,._. ... '< pm
99 .,
110
St
74" i -
: '
6
!... ..!
lon
pm
.8 1
..;. :.. ..:..._.9 4
io
., 121.9J
""'-127.2 ,
138 1
n
6
'
ss
12
200" Ra 8
IT
162
4.
i' 69 _:
6
58
12
18<
s
-r
'
76
4
31
Rb 1317c.'
6
83
1
s
43
Rb + 6
166
7 '
89
6
52
7
170 '8:
- :9S j
Pal+
6
118
8
11s s.-l 6 :,...:m : J
Pa
6
104
9
177
, 7 _. .} f
: 13S
8
li S
10
180
- - 8 - r 'r'r-: 140
6
92
ll
183
,9
;; l 4S
Pa''
8
105
12
186
10
y
9
109
14
197
12 ; t H.;1ss
4 PY
112
Re
6
77
Ta3
6
86
133
ReS+ 6
72
Ta
6 ._ll2 i
6
7
- -- 137__ Re6 _ 6 ______69__
."(t,3 _..._ _ 6_ _
,
8
143
Re7
4
S2
7
.
83 I
9
149
6
67
..
8 ' : -_ 88
10
IS4
Rh,.,. 6
80.S Thl+
.::..106.3
II
IS9
Rh4 + 6
71 k
I ,,.
12 j
12
163
Rll,. 6
69
" T
.118
4
3
Pb +
4
79
Ru
6
82
123.5,
S
87
Ru 6
76
Th4+
90
6
91.S Ru' 6
70.5 .
7
108
Ru .,. 4
S2
Tc
8
Pd 1 +
2
73 Rua. 4
2
2
Pd + 4 SQ
78 . S - 6
6
100
S.. 1 6
Pd3 + ' 6
90
g6+ ; i 4 . r
Pd...
6 .
a
7S.S , <>. , 6 .: .
Pm1 : 6 , . -.-'
u1
1 4J'Y
- 8 -r.t tl . ' 123 '
?.-\los
1. ;
.9
128.4 .. , 6
Po
6
108
Sb'+ 6
4
sn ,
i ,
il.
Cnntinurd
Size Effe cta
117
Table 4.4 (Confinu.Jj

Effective
ionic
the elements
racli of
lon
Ti
Ti1 +
n
1J)+
..Coo..cifta&n
II
12
6
6
4
..
6
8
6
8
12
4
6
Tm2
Tml
u,..
u-
Coorclincltion
pm
132
135
100
81
S6 .
113
184
89
102.5
117
123
102
113.4
119.2
116.5
103
109
114
pm
Jon
u,.
u6
9
12
6
7
2
119
131
yH
66
yl+
yl+
v-
112
6
6
8
9
6
6
7
numb.
6.5
74 ..5
88
164
yH
w
w>+
w
xe
6
7
8
6
6
s
6
8
4
5
6
6
6
4
5
6
4
...........
Coorclina1ion
lon
6
6
90
98
59
8
9
6
7
8
6
Yb2
9S
Yb3 +
100
93
78
67
Znl+
72
86
49.5
60
zr
68
80
76
56
65
74
S4
Values oC c.rystal radii frum Shannon. R. 0. Atta Crystallogr.
62
104
110
115.9
121..5
116
122
128
100.8
106..5
11:!..5
118.2
9
4
5
6
8
4
74
82
88
104
73
80
86
9:!
98
103
6
7
8
9
t976. IU2.
pm
751-767.
SQ square planer: PY pyrrunidal: HS ftiah spin; LS low spin.

' Huana. R. H .; Warcl. 0. L.; Dye. J. L. J . Atn. Chrm. Sr>c. 1989. Ill. S707-S708.
" Mudifted from
L. Now,. of thr Chrmit-al BnnJ. Jrd ed. : Cornel University:
Ithaca. NY. 1960. These values are only approximate.
even in simple ions-oflen becomes much worse. For example. one set of dara indicates that the radius of the ammonium ion is consistently 175 pm. but a diiTcn:nt
set indicates that it is the same size as Rb+, 166 ppm 21 This is not a serious discrepancy, but it is a disturbing one since its source is not obvious.
Yatsimirskiiu has provided an ingenious method for estimating the radii of polyatomic ions. A Born- Haber calculation utilizing the enthalpy of formation and related data can provide an estimate of the laltice energy. It is then possible 1o find
what value of the radius of the ion in question is consistent with this lattice energy.
These values are thus termed thermochemical radii. The most recent set of such values
is given in Table 4.5. In many cases the fact that the ions (such as COl- , CNS-.
CH,coo-) are markedly nonsphericallimits the use of these rndii Obviously they
21
Shannon. R. D. Am
1976. AJ1. 7SI.
u Yalsimirsltii, K. 8. l:u. AlaiJ. N(Jj/k SSSR. Ot.M. Kh;,n. Noult. 1941. 4S3; t948. 398. Sec also Mqos.
0 . M. P.; Rolt A. L /nofiJ. Cltem. 1991. JO. 3769- 371i . where Ihe shope or lhe lon is 1akcn imo conaider.uion u wdl u
t= Problem
11 1
4 lo"lllng Molle Ia In tnerg antc Che mistry : t. lonlc CompOuftlla
Thetmochemlcol rodli of
p.Jyelemlc ion
Jon
NH;
pm
Me4 N
PH;
oa;
BF;
BH4
BrO;
rn,coo-
ao;
ao;
CNCNs-
eoa:-
k>n
l SI
21S
171
281
296
218
179
140
148
IS7
226
177
199
164
30S
conCrFiCrO!CuC'l!Feet;
Gao;
Geel:GeFlHOi
HCOi
HCO.}
Hfi
HsHSe-
10)
JO.Fi
IrOl-
pm
Anlono
230
238
242
307
MnCJ:-
308
MnFlMnO;
N.}
242
344
Nco-
27S
314
2S2
187
NH 2CH 2C0i
NOi
NO)
Oi
ISS
142
ISS
193
191
108
163
221
OW
PbCIJ PdC'IlPrlltlPta!-
pm
Jon
Anlono
Anlono
AnlaM
AIO;
pm
k>n
Ccdlono
21S
181
189
176
178
16S
144
159
119
PtFlSbCI;
Se01SiFlSnBrlSnCl-
sru:-
SO!-
TiBrl-
334
r.a:-
30S
TiFl-
328
279
Vo!-
299
vo;
ZnBriZnO:Znl!-
282
328
337
22S
23S
24S
349
33S
382
244
338
317
21S
168
246
28S
272
309
Dala from .lcr!lcino. H. 0 . 8.; n..tur. K. P. J. Oonoo. Uur. 1979.$6, 316-m,..Jjuslaloo be

compaliblo wilh St.nnon- Prew\11 crys... tlldii. Uucl ...., pcnnb:olon.
can be reinserted into rurtber thermochemical calculations and thus provide such
data as the anticipated lauice energy of a new (sometimes hypothetical) compound.
In the case of tetrahedral and especially octahedral ions, the symmerry is sufficiently high that the ions may be considered pseudospherical. und so t he vulucs
more dosely represent the physical picture !hat we have of ionic radii.
Efficiency of Packing
and Crystal Lattices
lr we consider atoms and ions to be hard spheres, we find that there ;trc cenain
geometric arrangements for packing them which are more efficient than orhcrs. This
can be confirmed readily in two dimensions with a handful or coins. For example. if
a set or coins or the same size (dimes, for example) is arranged. it will be found that
six of them fit perfecUy around another (i.e., touching each other and the central
dime), giving a coordination number of 6. However, only five qwmers or four silver
dollars will fit around a dime,14 illustrating the importance or size in determining
the optimum coordination number. Tile effect of charge can also be illustrated. If all
of the atoms are the same, the most efficient two-d imensional lattice is the closest
packed. six-coordinate arrangement. If they are or the same size but opposire charge,
the six-coordinale structure is not stable since it will have too many repulsions or
like-charge ions. This Cln also be readily shown with coins (using hcuds and tails to
> The fit is nDI eud In lhc lUter IWO c:ues.
Siae Ellech
<I
(b)
119
(c)
Fig. 4.11 Two-dimensional lattices: (a) SJable, six-<:oocdinate, closest packed Janice
of uncharged atoms; (b) unstable, six-coordinate lattice of charged ions; (c) stable,
four<oordinate lattice of charged ions.
t'
(b)
Rg. 4.12 (a) Sites created by layer I and available to accept atoms in layer 2. (b) Covering
aU t sites by atoms in the second layer. making the r' sites (relabeled o) unavailable for
oa:upancy by close-packed atoms.
represent charge). and it can be seen thut the most stable arr.snsement is a square
lattice of
charge (Fag. 4. 11C).
The same principles hold for three-dimensional lauioes. Consider first a lattice
composed only of uncharged atoms as in a metal or a crystal of noble gas atoms.
The first layer will consist of a
closest p-.tckcd layer (Fig. 4.11a). The
second layer will be of the same type but centered over the
that exist
where three atoms in the first layer come in contact (Fig. 4.12a).u A layer containing
n atoms will have 2n such sites capable of accepting atoms (marked t and r'), but
once an atom has been placed in either of the two equivalent sets (t and () the
remainder of that layer must continue to utilize that type of site (Fig_ 4.12b), and
the remaining n sites (labeled o) are not utilized by the packing atoms.
The third layer again has a choice of n sites out of a possible 2n available (t and
( types
One alternative places the atoms of the third layer over those of the
first; the other places the atoms of the third layer over the o sites of the first layer. In
The reoder b acrongly uraed to build these structures usins Styro(oam Sflhercs end to consuu teats
on structural chemistry such as Wells, A. F. Stntawd lnorgalllc O.tmlstry, Sch eel.; 1984; TN TltUd
Dfmnuion It! CMmlstry, Clarendon: o.lorcl. 19.56. The present discusolon mc:n:ly presents the mon:
salient fcalurcs or the subject
120
4 aondlng Model a In tnorsaanlc Chemhtry: I. Ionic Compounds
Fig. 4.13 Arrangement of

layers in hexagonal closest
paclced (a) and cubic closest
8
A
packed (b) Structures. lbesc

are "side views" compared
with tbe "top views" shown
in the preceding figures.
8
A
(I I
(bl
the first type the layers alternate ABABAB and the lattice is known as the hexagonal
closest packed (hcp) system. Alternatively. the cubic closest packed {ccp) system has
three different layers, ABCABC. Both lattices provide a coordination number of 12
and are equally efficient at packing atoms into a volume.
It is easy to see the unit cell and the origin of the term hexagonal dosest packed.
In Fig. 4.!3a the unit cell can be constructed by drawing a hexagon through the
nuclei of the six outer atoms in layer A aDd a parallel hexagon in the next A layer
ubove. and then connecting the corresponding vertices of the hexagons with perpendicular lines to form a hex:1gonal prism (Fig. 4.13a).
One could follow a similar practice and construct a similar hexagonal "sandwich" with two layers (B, q of "filler," but a cubic cell of higher symmetry can be
constructed; the second system is thus characterized as cubic closesr packed. The relation be,tween the cubic unit cell {which is identical to the face-centered cubic cell we
seen) is not easy to visualize unless one is quite familiar with this system.
have
The
way is to
a face-centered cubic array (Fig. 4.14c). and by removing
(D)
(b)
(<I
(d)
Fig. 4.14 Unit cells in the cubic closest packed systems. (:1) A face-centered array of atoms. Note that the exposed layer
consists of a closest packed array or fifteen atoms. Consider this the A layer. (b) A closest packed layer of six atoms
placed on (a). Consider this the a layer. (c) The final atom. a member of lhe c layer: is added to complete the
cube. The /cc unit ceO is redrawn in (d). Note that the sinale atom that composes the c layer does not lie above any arom
in lhe A layer (as it would if lhis were
Stu ElfecJ
121
an atom (Fig. 4. 14bl. then a few more (Fig. 4.14a), reveal the closest packed layers
corresponding to A. B, and C in Fig. 4. 13b.
The noble gases and most metals crystallize in either the hcp or the ccp structure
as would be expected for neutral atoms. The alkali metals, barium, and a few transition metals crystallize in the body-centered cubic system, though the reasons for this
choice are unknown.
If all the packing atoms are no longer neutral (e.g., half are cations and half are
anions). the closest packed structures are no longer the most stable, as can be seen
from the similar two-dimensional case (see above). However, these structures may still
be useful when considered as limiting cases for certain ionic crystals. Consider lithium
iodide, in which the iodide anions are so much larger than the lithium cations that
they may be assumed to touch or nearly touch. They can be considered to provide
the framework for the crystal. The much smaller lithium ions can then fit into the
small interstices between the anions. If they expand the lattice slightly to remove the
anion-anion contaa, the anionic repulsion will be reduced and the crystal stabilized.
but the simple model based on a closest packed system of anions may still be taken
as the limiting case and a useful approximation.
Where the lithium ions fit best will be determined by their size relative to the
iodide ions. Note from above that there are two types of interstices in a closest packed
structure. These represent tetrahedral (r) and octahedral (o) holes because the coordination of a small ion fitted into them is either tetrahedral or oaahedral (see
Fig. 4.12). The oaahedral holes are considerably larger than the tetrahedral holes
and can accommodate larger cat.ions without severe distortion of the structure. In
lithium iodide the lithium ions fit into the octahedral holes in a cubic closest packed
lattice of iodide ions. The resulting structure is the same as found in sodium chloride
and is face-centered (note that face-centered cubic and cubic closest packed describe
the same
Consider a closest packed lattice of sulfide ions. Zinc ions tend to occupy tetrahedral holes in such a framework since they are quite small (74 pm) compared with
the larger sulfide ions (170 pm). If the sulfide ions form a ccp array, the resulting
structure is zinc blende; if they form an hcp array, the resulting structure is wurtzite.
See Fig. 4.1 5.
Although in the present discussion size is the only parameter considered in determining the choice of octahedral versus tetrahedral sites, the presence of covalent
bonding (d 2sr versus sp 3 hybridization. see Chapter 5) and/or ligand field stabilization (see Chapter II) can affect the stability of ions in partiCular sites. Size will usually
be the determining factor when these additional factors are of small importance--for
example, when considering alkali and alkaline earth ions. The coneept of dosest
packing of anions is also very useful in considering polar covalent mncromolecules
such as the silicates and iso- and heteropolyanions.:u.
If the cations and anions are of approximately the same size, the limiting case of
the framework being determined by the larger ion is inappropriate, and we simply
determine the most efficient lattice for oppositely charged ions of equal size. This
turns out to be the CsC!Iattice, which maximizes cation-anion interaction (C.N. = 8)
and is the most stable structure when the sizes of the cation and anion are comparable.
Wells, A. F. Strucwrallnorgonic CMml.rry. Sth eel.; Clarendon: Ox!ord. 1984. For a comprchonsive
and dclaited cllscussion of the broad usefulness of classifying structures in tern\$ of clo<eslpecked
see Dooglas, B. E.; McDaniel D. H.; A1cunder. J. J. Concepts and Mode& of lnorgonic
Wiley: New Yortc. 1983; pp 198- 208.
Chemistry. 2nd
122
4 lotullnlf Modela In lnorgentc Che111istry: t. l onlc Corwpeunda
lbl
(a)
Fig. 4. 15 (u) The

d wunzite. The sulfide ions fonn :sn lkp uiTlly with A lgr:>y)
und B !black) alternating luyen (Cf. Fia. 4. 13n}. (b) The srruct ure of line blen<le. The sullide
ions fonn a ccp :trrny with A (white). B (black), :IOd C (Siuyl byen. (Cf. Fi{:s. 4.13b :JJ'ld
4. 14.) Note th:u in both Slruc:turcs t he line atOll\$ (smu/1 white cit'tles) occupy tclr,hcdr.tl
holes.
Radiu5 Ratio
h is not difficult to calculate the size or the octahedral hole in a lattice or closest
packed anions. Figure 4.16 illustrates the geometric arr:tngement resulting from six
anions in contact with each other and with o cation in the
hole. Simple
geometry allows us to fix the diagonal of t he square us 2r _ + 2P . The angle form.:<!
by the diagonal in the corner must be 45, so we can say:
.,.....-2r...;;-=-- = cos 45 = 0. 707

2r_ +2r.
r _ = 0.707r _
(4.21)
+ 0.707r.
(4.22)
n
- -.-
0,'
(I )
(b)
Fig. 4.16 (a) Small cation

(dashed line} in oanhedral
hole formed by six anions.
(b) Dissection or ocuhedron
2r.
_..1/.t
7,.,:
f
(le4.6
Radlu.
nnd
coordlnallon numb
Coortf....tion
""""""'
4
Geometry
Tetrahedral
Octahedral
Cubic
Olboctohedral6
12
IJmillng radius
ratio
0.414; 2.42
0.732; 1.37
1.000
Possi>le lattKe
lhvctwes
Wurttite, zinc blende_/
NaCl, rutile
CsCI, fluorite
" The S<:COUd ratio !s merely the recipl'OClll or the first. It is often convenient to
have bolh values.
" The aJoms in !he lop Jhrec layers of F'11. 4.1Jb form a c:uboctohedron.
' Cootdinallon number 12 is DOl found in simple ionic aystals. It oc:curs in
complex meJat oxides end in c:losesl packed Jaui<:... or aiOms.
0.293r.
= 0.7CJlr +
(4.23)
'+
= 0.293 =0.414
r.
0.707
(4.24)
This will be the limiting ratio since a cation will be stable in an octahedral
hole only if it is at least large enough to keep the anions from touching. that is,
r ./r _ > 0.414. Smaller cations will preferentially fit into tetrahedral holes in the
lattice. By a similar geometric C.llculation it is possible to determine that the lower
limit for tetrahedral coordination is r ./r_ .. 0.225. For radius ratios ranging from
0.225 to 0.414, tetrahedral sites will be preferred. Above 0.4 14, octahedral coordination is favored. By similar calculations it is possible to find the ratio when one
cation can accommodate eight anions (0.732) or twelve anions
A partial list
of limiting radius ratio values is given in Table 4.6.
The use of radius ratios to rationalize structures and to predict coordination
numbers may be illustrated as follows. 17 Consider beryllium sulfide. in which
'nc> .frs =59 pmfl70 pm = 0.35. We should thus expect a coordination number
of 4 as the Bel+ ion fits most readily into the tetrahedral holes of the closest packed
lattice. and indeed this is found experimentally: BcS adopts a wurtzite structure.
In the same way we C.ln predict that sodium ions will prefer octahedral holes in
a closest packed lattice of chloride ions (r" frc 1- = 116 pm/167 pm 0.69), forming
the well-known sodium chloride lattice with a coordination number of 6 (Fig. 4.1a).
With larger cations, such as cesium. the radius ratio (rc,fr0 = 181 pm/
167 pm
1.08) increases beyond the acceptable limit for a coordination number of
6; the coordination number of the C.ltions (and a nions) increases to 8, and the cesium
chloride lattice (Fig. 4.1 b) results. As we have seen, although this is an efficient structure for cations and anions or about the same size, it cannot be directly related to a
closest packed structure of anions.
Table 4.6 indicates that a coordination number of 12 should be possible when
the radius ratio is 1.00. Geometrically it is possible to fit 12 atoms about n central
11
Sina: c:tySlal flldij vary sli&hUy wilh coordinaJion

CN. = 6 as "aV<:rage" values.
values (rom Tal* 4.4 were Jalccn for
124
4 Bonding Modela In Inorganic Chemhby: 1. Ionic Compovn4a
Rg. 4.17 The total energy of a cubic lattice of rigid anions and cations as a function of r +
with r _ fixed. for different coordination configurations. When the anions come into mutual
contact as a result of decreasing r. their repulsion determines the lattice constant and the
cohesive energy becomes constant when expressed in terms of r __ Thus near the values of
r.!r_ at which anion-anion contact takes place, the radius ratio model predicts phase
transitions to structures of successively lower coocdination numbers. Note that the
in the curves correspond to the values liSted in Table 4.6. [From Treatise on Scful State
Hannay. N. B, Ed.; Plenum: New Yorlc, 1973.)
ntom (see the discussion of closest packing in metals, page 119). but it is impossible
to obtain mutual twelve-coordination of cations and anions because of the limitations
of geometry. Twelve-coordination does occur in complex crystal structures or mixed
metal oxides in which one metal acts as one of the closest packing atoms and others
lit into octahedral holes. but n complete discussion of such structures is more appropriate in a book devoted to the structures of solids.lll
The change in coordination number as a result of the ratto of ionic radii is
shown graphically in Fig, 4.17. In general, as the cation decreases in size the latt.ice
is stabilized (lattice energy becomes more negative) until anion-anion contact occurs.
Further shrinkage of the lattice is impossible without a reduction in coordination
number; therefore. zinc sulfide adopts the wurtzite or the zinc blendc structure.
gaining additional energy over what would be possible in a structure with a higher
coordination number. Note that although there is a significant difference in energy
between structures having coordination numbers 4 and 6, there is little difference
between 6 and 8 (the two lines almost coincide in Fig. 4.17 on the !eft).10e difference
in energy between six- and eight-coordinate structures is less than 1% based on
e.lectrostatics.
In a I: 1 or 2:2 salt, the appropriate radius ratio is obviousiy the ratio of the
smaDer ion (usually the cation) to the larger to determine how many of the latter will
lit around the smaller ion. In compounds containing different numbers of cations
and anions (e.g., SrF2 , TiO, Li 20, Rb2 S) it may not be immediately obvious how
to apply the ratio. In such cases it is usuaUy best to perform two calculations. For
11
S..: Wells, A. F. Sttv<twrol
Slh
Oforcl. 1984; pp 480-sa<J.
Slu 111<1
125
example, consider SrF2 :

132
= 1.11
119
rs." =
rF-
.!!:... =
132
r 5,,.
maximum C.N. of Sr2 = 8
= 0.90 maximum CN. ofF - .. 8
Now there must be t wice as many fluoride ions as strontium iOilS, so the coordination
number of the strontium ion must be twice as large as that of fluoride. Coordination
numbers of 8 (Sr+) and 4 (F- ) are compatible with the maximum allowable coordination numbers and with the stoichiometry of the crystal. Strontium fluoride
crystallizes in the fluorite lattice (Fig.
A second example is Sn01 :
rs..
ro -
Tot-
's-.
126
= 0.66
= 126 = 1.52
83
maximum CN. of Sn4

maximum CN. of 0
2-
= 6
Considering the stoichiometry of the salt, the only feasible arrangement is with
C .N-o- = 3, CN-s. 6; tin dioxide assumes the Ti02 or rutile structure of Fig. 4.4.
Note that the radius ratio would allow three more tin(IV) ions in the coordination
sphere of the oxide ion, but the stoichiometry forbids it.
One final example is K 2 0:
152
= 1.21
126
maximum CN. of K +
126
= 0.83
152
maximum CN. of
!!:... =
T()l-
Tot-=
rK.
..
oz- - 8
Considering the stoichiometrY of the salt, the structure must be antifluorite (Fig. 4.3.
reversed) with C.N.0 ,_ = 8, C .N.K. - 4.
The radius ratio quite olten predicts the correct coordination numbers of ions in
crystal lattices. ll must be used with caution, however, when covalent bonding becomes imponant. The
may have been puuled as to why beryllium sulfide was
chosen to iUustrate the radius rotio rule for coordination number 4 (page 123) instead
of zinc sulfide, which was used repeat edly earlier in this chapter to illustr.lle fourcoordinate structures such as wurtzite and zinc blende. The reason is simple. If ZnS
had been used, it would have caused more confusion than enlightenment II violates
the radius ratio rule! Proceeding as above, we have r +/r _ = 88 pmfl70 pm = 0.52,
indicating a coordination number of 6, yet both forms of ZnS, wurtzite and zinc
blende, have a CN. of 4, for both cations and anions.. If one argues that 0.52 does
not differ greatly from 0.41, the point is weD taken, but there exist more vexing cases.
The radius ratio for merc:ury(ll) sulfide. HgS. is 0.68. yet it crystallizes in the zinc
blende structure. In both or these examples the
hybridized C'OI'(J/en/ bonding
seems to be the dominant factor. Both ZnS and especially HgS are beuer regarded
as infinite covalent lattices (see Chapter 7) than as ionic lattices.
126
4 loclln1
1111 lnerponlc Chmlatry: I. loftlc Cem,evnllla
It should be kept dearly in mind that the radius ratio rules apply strictly only to
the packing of hard spheres of known size. As this is seldom the case, it is surprising
that the rules work as well as they do. Anions are not "hard" like billiard balls, but
polarizable under the influence of cations. To whatever extent such polarization or
covalency occurs, errors are apt to result from application of the radius ratio rules.
Covalent bonds arc directed in space unlike electrostatic attractions, and so certain
orientations are preferred.
There are, however, Other exceptions that are difficult to attribute to directional
covalent bonds. The heavier lithium halides only marginally obey the rule, and perhaps a case could be made for C.N . .. 4 for lil (Fig. 4.18). Much more serious,
however, is the problem of coordination number 6 versus 8. The relative lack of
eight-coordinate structures-Csa, CsBr, and Csl being the on ly known alkali metal
examples-is commonly round, if hard to explain. There are no eight-coordinate
lSO
/,
200
...
NAO structurt
CsCIIIN<Wte
0 bolh Noel"""
Cs0 St NC,URS
r, (pm)
Rg. 4.18 Actual crysaal saructures or the alkali halide$ (as shown by the symbols) contr:wcd
wiltl the predictions ol the radius ratio rule. The figure is divided into three rqions by the
line$ r./r_ -0.414 al'ld r.tr_ 0.732, predicting coordinntion number 4 (wuruite or zinc
blende, upper left), coordination number 6 (roclc sal a, NaO. middle). al'ld coordination
number 8 (CsCI.. lower
The crystal111dius ollithium, and to a lesser ctent that or
sodium, changes with coordination number, 10 both the radii with CN. - 4 (lert) al'ld
CN. - 6 (right) haw: been plotted.
The Prelllcllve Pow er of Ther,.ochomlcel Clcut.aloftt Oft Ionic Compoun lla
127
oxides. MO. even though the larger divulent metal ions. such as Sr2+. Ba1 +, and
Pb:+, are large enough that the radius ratio rule would predict the CsCI structure. There is no simple explanation for these observations. We have seen that the
Maclelung constant for C.N. = 8 is only marginally larger than that for C.N. 6.
Thus small energies coming from other sources can tip the balance.
The r.1dius ratio is a useful, lhoul!h imperfect, tool in our a rsenal for predicting
a nd understanding the behavior of ionic compounds.19 From a theoretical point of
view it rationalizes the choice of lattice for various ionic or partially ionic compounds.
Its fa ilings call our attention to forces in solids other than purely electrostatic ones
acting on biOiard-ball-like ions. We shall encounter modifications and improvements
of the model in Chapter 7.
The Predidive
Power of
Thermochemical
Calculations on
Ionic Compounds
The following example will illustrate the way in which the previously discussed
parameters, such as ionic radii and ionization energies, can be used advantageously
to explore the possible existence of an unknown compound. Suppose one were interested in dioxygc:nyl tetralluoroborate. (01 ]+[BF4 ) -. At first thought it might
seem an unlikely candidate for existeoce since oxygen tends to gain electrons rather
than lose them. However, the ionization energy of molecula r oxygen is not excessively high (1165 kJ mor 1; cf. Hg. 1009 kJ mor 1), so some trial calculations might
be made as follows.
T he first values necessary are some estimates of the ionic radii oro; and BF4.
For the latter we may use the value obtained thermochemically by Yatsimirskii.
218 pm. An educated guess has to be made foro;, since if we arc: attempting to
make it for the first time (as was assumed
we will not have any experimental
data available for this species. However, we note that the CN- ion, a diatomic ion
which should be similar in size, has a thermochemical radius of 177 ppm. Furthermore, an estimate based on covalent and van der Waals radii (see Chapter 8) gives
a similar value. Because o;- has lost one electron and is positively charged. it will
thus take 177 pm as a conservative
probably be somewhat smaller than this. We
estimate; if the cation is smaller than this, the compound will be more stable than
our prediction and even more likely to
Adding the radii we obtain an estimate
or 39.S pm for the interionic distance.
Next the lauioe energy can be calculated. O ne method would be to assume
that we know nothing about the probable structure and use the Kapustinskii equation (Eq. 4.20) and r 0 395 pm. The resulting lattice energy is calculated to be
-5S5 kJ mol- 1
Alternatively. we might examine the radius ratio oro; BF; and get a crude estimate or ffi 0.8. The acruracy or our values does not permit us to choose between
coordination number 6 and 8, but since the value of the Madelung constant does
not differ appreci:tbly between the sodium chloride and cesium chloride struetures, a
value of 1.75 may be ta.ken which will suffice for our present rough calculations. We
may then use the Bom-Lande equation (Eq. 4.13). which provides an estimate or
-616 kJ mol- 1 for the
energy, which will be decreased by about 10"/. (if
An anii,.Z rl 227 compounds indicaltcl ahol lhc ndiUl ratio Nle WOftcd
cxne.
J. CMm. Ul<.
Jroublesome wen Gr-ouj) tB(II)and 118112)
19M. 61,1tS-118.
M>out IWO-Ihircls rllbc

lice H&S- Nal ha.n, LC
J 28
4 8on.lng Mo.oh In lnorvanlc Chomlalry: J. Ionic Compounds
n = 10) to 200/o (if n = 5). The two calculations thus agree that the lattice energy will
probably be in the range -480 to -560 kJ mor- (-liS to -134 kcal mol- 1). This
is a quite stable lattice and might be sufficient to stabilize the compound.
Next we might investigate the possible ways of producing the desired compound.
Because the oxidation of oxygen is expected to be difficult to accomplish we might
choose vigorous oxidizing conditions, such as the use of elemental fluorine:
(4.25)
It is possible to evaluate each term in a Bom- Haber cycle based on Eq. 4.25.
The usual terms we have encountered in previous Born- Haber cycles may be
evaluated readily:
Ionization energy of 0 1 = 1165 kJ mol- 1
Dissociation of !F1 = 79 kJ mot-
Electron affinity of F
-328 kJ mot
One additional term occurs in this Bom-Haber cycle: the formation of the tetrafluoroborate ion in the gas phase:
BF31a1 + Fi81 -
(4.26)
Fortunately, the enthalpy of this reaction has been experimentally measured30 to be

-423 kJ mol- 1 Adding in the value of -500 20 kJ mol-' for the lattice energy
provides an estimate of the heat of the reaction in Eq. 4.25 that is essentially zero.
This JS somewhat discouraging. since if Eq. 4.25 is not exothermic, entropy will drive
the reaction to the left because all of those species are gases, and dioxygenyl tetrafluoroborate would not be expected to be stable. RecalL however, that our estimates
were on the conservative side. We would therefore expect that dioxygenyl tetrafluoroborate is either energetically unfavorable or may form with a relatively low
stability. It certainly is worth an attempt at synthesis.
In fact, dioxygenyl tetralluoroborate has been synthesized by a reaction similar
to Eq. 4.25, although in two steps: the formation of intermediate oxygen fluorides and
then combination with boron trifluoride. 31 It is a white ceystalline solid that slowly
decomposes at room temperature. Energy
of this type are exceedingly
useful in guiding research on the synthesis of new compounds. Usually it is not necessary to start with the complete absence of knowledge assumed in the present example.
Often one or more factors can be evaluated from similar compounds. It was the
observation of the formation of dioxygenyl hexalluoroplatinate(V) and similar calculations that led Bartlett to perform his first experiment in an attempt to synthesize
compounds of xenon. This successful synthesis overturned prior chemical dogma (see
Chapter 17).
Now that we have seen that dioxygenyl compounds can be prepared, we might
be interested in preparing the exotic and intriguing compound dioxygenyl superoxide, 0;02. Using methods similar to those discussed above, we can set up a
10 Srivastava,
R. D.; Uy, 0 .
Fort>er, M. J. Chtm. Soc., FuraJoy TroJU. I 1974, 70, 1033.
" Keith, J. N.; Solomon, I.J.; Shdl, 1.; Hyman, H. H. IM<g. Clwm. 1968, 7, 230-234. CiociSChcl CT.; :
Campanile, V. A:, Wagn<r, CD.; Wilson, J. N.J. Alii. Chcm. Soc. 1969, 91,4702-4707
j
. --"'
Covalent Character In Pre4omlnandy Ionic lon4a
r!Sa
\J..:/
... _ ' '
(II
129
,------,\l
/I
"... ___
(cj
(bl
Fig. 4.19 Polarization

(a) idealized ion pair with no polarization, (b) mutually
polarized ion pair. (c) polarization sufficient to fonn covalem bond. Dashed lines represenJ
hypothe1ical unpolarizcd ions.
Born- Haber cycle and evaluate the following terms.
02 o; + e02 + e----+ 01
Lattice energy
t..H = 1165 kJ mol- 1

t..H = - 42 kJ mol- 1
t..H -500 kJ mol - 1
+623kJmol - '
The calculations support our intuitive feelings about this compound. If it were
somehow possible to make an ionic compound 0i02. it would decompose with
the release of a large amount of energy:
OtOi - - + 20z
t..H
-623 kJ mol- 1
Dioxygenyl superoxide is not a likely candidate for successful synthesis.
Covalent Character
in Predominantly
Bonds
It is probable that every heteronuclear boad the chemist has to deal with contains a
mixture of covalent and ionic character. Ordinarily we speak glibly of an ionic compound or a covalent compound as long as the compound in question is predominantly
one or the other. In many cases, however, it is convenient to be able to say something about intermediate situations. In general, there are two ways of treating ioniccovalent bonding. The method that hos proved most successful is to consider the bond
to be covalent and then consider the effect of increasing charge displacement from
one atom toword another. This method will be discussed in the next chapter. Another
method is to consider the bond to be ionic and then ollow for a certain omount of
covalency to occur. The second method was championed by Kasimir Fajans12 in
his quanticule theory. The latter theory has found no place in the repertoire of the
theoretical chemist largely because it has not proved amenable to the quantitative
calculations which other theories have developed. Nevertheless, the quabtative ideas
embodied in kFajans' rules" offer simple if inexact approaches to the problem of
partial covalent character in ionic compounds.
Fajans considered the effect which a small, highly charged cation would have on
an anion. If the anion were large and "sofi" enough, the cation should be capable of
polarizing it, and the extreme of lhis situation would be the calion actually penetrating the anionic electron cloud giving a covalent (shared electron) bond (Fig. 4.19).
n F'IJGns. K. Narwwi$.,nscho/ltn J91J. II. 165. For a more recent di1CU$.'ion of Jhc same subjecl. see
Fajans, K. Struct. &ndin11 B.rlin 1967, J. 88-JOS. For an inlereslirc short sl<ek:h on Jhc Jhcory und lhc
man ..., Hwwic. J . J.
d,c. tm. 64. 122.
1 30
4 l o nllll n8
111 Inorgani c Chiatry1 1. lo 111c CoMpovnlll a
Fajans suggested the following rules to estimate the extent to which a cation could
polarize an anion and thus induce covalent character. Polarization will be increased
by:
!. High charge and small size if rhe cation. Small. highly charged cations will
exert a greater effect in polarizing anions than large and/or singly charged
cations. This is often expressed by the Ionic poCtlllla/ 33 Of the cation: 4l = Z +Jr.
For some simple ions, ionic potentials a re as follows (r in nm):
= 7
Cal+ "' 18
Gal 49
or
Obviously there is no compelling reason for choosing Z/r instead

Z/r'or several other functions that could be suggested, and the values above are
meant merely to be suggestive. Nevertheless, polarization docs follow some
charge-to-size relationship, and those cations with large ionic potentials are
those which have a tendency to combi.ne with polarizable anions to yield
partially covalent compounds. The iooic potentials listed also rationalize an
interesting empirical observation indicated by the dashed arrows: The first
element in any given family the periodic chan tends to resemble the second
element in the family to the righL Thus lithium and magnesium hove much
in oommon (the best known examples are the organometallic compounds of
these elements) and the chemistry of beryllium and aluminum is surprisingly
similar despite the difference in preferred oxidation state.J This relationship
extends across the periodic chan; for
phosphorus and carbon resemble each other in their elcctronegativities (see Chapter
A word should be said here concerning unusuaDy high ionic charges often
found in charts ionic radii. Ionic radii are often listed for Si.... pH, and
even a 7 . Although at one time it was popular. especially nmong
to discuss silicates, phosphates. nnd chlorntes though they contained these
highly charged ions, no one today believes that such highly charged ions hnve
any physical reality. The only possible meaning such rndii can have is to indicate that if an ion such as P' + or Cl' + could
its high charge combined
with small size would cause it immediately to polarize some adjacent anion
and form a covalent bond.
2. High charge a11d Iorge size r/the anion. The polarizabili ty of the anion will
be related to its "softness," that is, tO the deformability its electron cloud.
Both increasing charge and increasing size will cause this cloud to be tess
under the influence of the nuclear charge oC the anion and more easily influenced by the charge on the cation. Thus large anions such as I -, Se1 -, and
or
or
or
, CutJocl&c, G. H. J. Am. a-. Sclc. 1911. j(J, USS. 2863; ibid. 1930. J1. l076.
.. ll is troc lhol Jhe valueoflhc loaicpolcnliol ofU is closet lo INll oiCa' 1haft10 IMI ofMa'.anct
strnna arsumcna bu been made lhel Li raembles Ca" mort 1hon Ml'" ( Hanusa. T. P. J. Cllml.
EJuc. 1917, 64, 686.] The IKt"'lh d the Fajans approach and abe rmJtd idea of diasonaltescmblancc
rests on ias qud/IIJI&Jt SU<C<SS. The dlaaonal rule and ahe ionic: poecnlial should be wed as grJJn rather
lhan as JUbstinlles ror close inspection of eadl
siluallon.
Covel e nt Chercl el' 1n Pre4eMifteftJiy l eal c l oruh
131
Te2 - and highly charged ones such as

and pl - are especially prone to
polarintion and covalent character.
A question naturally occurs: What about the polarization of a large cation
by a small anion? Although this occurs, the results are not apt to be so spectacular as in the reverse situation. Even though large, a cation is not likely
to be particularly "soft" because the cationic charge will tend to hold on to
the electrons. Likewise. a small anion can tend to polarize a cation, that i.s,
repel the outside electrons and thus make it possible to "see" the nuclear
charge better, but this is not going to lend to covalent bond fomJation No
convincing examples of reverse polarization have been suggested.
3. Electron eotifigurDJion of the cation. The simple fom1 or the ionic potential
considers only the net ionic charge of the ion with respect to its size. Actually
an anion or polarinble molecule will feel a potential resulting from the total
positive charge minus whatever shielding the electrons provide. To use the
ionic charge is to assume implicitly that the shielding of the remaining
trons is perfect, that is, 100"/o effective. The most &erious problems with this
assumption occur with the transition rnetnl ions since they have one or more
d electrons which shield the nucleus poorly. Thus for two ions of the sa.me
size and charge, one with a n (n- l)d"ns0 electronic configuration (typical of
the transit.ion elements) will be more polarizing than a cation with a noble
gas configuration (n- l)sl (n - l)p6 nf! (alk.ali and alkaline
metals, for
example). As an e.xample, HgH has an ionic radius (C.N. = 6) of 116 pm. yet
it is considerably more polarizing and its compounds are considerably more
covalent than those ofCa1 with almost ident.ical size (1 14 pm) and the same
charge..
Results of
Po larization
One of the most common examples of covalency resulling from polarization can be
seen in the melting and boiling points or compounds of various metals." Comparing
the melting points of compounds having the same anion, but cations of different size,
we have BcO, = 405c, CaCI 1 - 782 C; for cations of different charge. we have
NaBr = 74JOC. MgBr 1 1ooc, AIBr, .. 97.5 c: for a constant cation. bu t :mions
of different sizes, we have LiF = 84s e, LiO =- 605 "C. LiBr = 5SO"C. Li l = 449' C:
and fo r ions huving the same size and charge; the ciTcct of electron configuration can
be seen from CaCI1 782 c, HgCJ 1 ... 276 c. Care must be taken not to interpret
melting points and boiling points too literally as indicutors of the degree of covalent
bonding; there a re many effects operative in addition to covalency and these will be
discussed at some length in Chapter 8.
A second area in which polarization effects show up is the solubility of salts in
polar solvents such as water. For example, consider the silver halides. in which we
have a polarizing cation and increasingly polarizable anions. Silver fluoride, which is
quite ionic, is soluble in water, but the less ionic silver chloride is soluble only with
the inducement of complexing ammonia. Silver bromide is only slightly soluble and
silver iodide is insoluble even with the addition of ammonia Increasing covalency
from fluoride to iodide is expected and decreased solubility in water is observed.
"One learns in I<"Cf''O chcmisuy C<>Unt:S thal ionoc
h:ooc 1\iab mcllina poinu and cow:aktu
ones '-c low flldli"8 poinu. At1houch tiU OYCtSOmplificallon con be
iJ ltlily be :sppiJcd 10
the present discussicn A more Jhoroooch discussion ol1he faaon onvolwd on mdlina and bcloli._ poiniS
wil be l'ound in Qap<<r L
ITalk:ld,..
132
4 l u .. lnl Mo .. ola In lnorgnn l c Chom h lry : 1 . l u t e CoMpoun .. a
Fig. 4.20 Hydr:llion

energies as a function of
size and charge of cations.
(From Philips, C. S.
Williams, R. J. P. lncrgcnl
Clemistry. Clarendon:
Oxford, 196S. Reproduoed
with permission.]
-1100
-1000
-900
-800
0'
E -700
-a
-600
Silver halide
Silver fluoride
Silver chloride
Silver bromide
Silver iodide
Soluble
2
X J0 - 10
X JO - U
s x w - 17
As in the case of melting points, solubility is a complex process, and there are many
factors involved in addition to covalency.
Oosely related to solubility are the hydration cnthalpies of ions. It has been
found 36 that it is possible to correlate the hydration enthalpies of cations with their
"effective ionic radii" by the expression (see Fig. 4.20)
6H = -69,500(Z1{r.,,) kJ mol- 1 (r.rr in pm)
'"l.alimor, W.
Pitur, K. 5.; sauuky. C M. J. Ch""" Pftys. 1939, 7, 108-tll.
(4.27)
In this case the reason tor the correlation is fairly obvious. The parameter rcf! is
equal to the ionic radius plus a constant. 85 pm, the radius of the oxygen atom in
water. Therefore, reM is elfectively the interatomic distance in the hydrate, and the
Born-Lande equation (Eq. 4.13) can be applied.
A third, and perhaps the most fundamental, aspect of polarization can be seen
in the bond lengths of silver halides. If we predict these distances using the ionic
radii of Table 4.4, our accuracy decreases markedly in the direction AgF > AgCI >
AgBr > Agl:
+ ,-
Compound
AgF
AgCJ
AgBr
Agl
248
296
311
320
r ,
246
277
289
281
- 2
-19
- 22
- 39
The ShanDon-Prewitt ionic radi i (r+ + r-) an: based on the most ionic compounds,
the fluorides and oxides for the radii of the metal cations, and the alkali halides for
the radii of the anions of the remaining halides. 11le shortening of silver halide bond
lengths is attributable to polarization and covalency.
The basis for other correlations between size, charge, and chemical properties is
not so clearcul Chemical rtactions can often be rationalized in terms of the polarizing
power of a particular cation. In the alkaline eanh carbonates, for example, there is
a tendency toward decomposit.i on with the evolution of carbon dioxide:
MC03 - - + MO + C02
(4.28)
The ease with which this reaction proceeds (as indicated by the temperature necessary
to induce it) decreases with increasing cation size: BeC03 unstable; MgC03, 350 OC;
CaC0 3 , 900e; SrC0 3 , 1290e; BaC0 3 , 1360c The effect of d electrons is also
clear: Both CdC0 3 and PbC0 3 decompose at approximately
despite the fact
that Qll+ and Pbl+ arc approximately the same size as Cal+. The decomposition
of these carbonates occurs as the cation polarizes the carbonate ion, splitting it into
an 0
ion and
Stem 31 has extended the qualitative argument on decomposition by showing
that the enthalpies of decomposition of carbonates, sulfates, nitrates, and phosphates
are linearly related to a charge/size function, in this case r 1' 2/Z* (see Fig.
Although the exact theoretical basis of this correlation is not clear, it provides another interesting example of the general principle that size and charge are the imponant factors that govern the polarizing pOwer or ions and, consequently, many
of their chemical properties.
From the preceding, it might be supposed !hal covalent character in predominantly ionic compounds always destabilizes the compound. This is not so. InStability
results from polarization ofthe anion causing it to spli t into a more stable compound
(in the above cases the oxides) with the release of gaseous acidic anhydrides. As will
be seen in Chapter 16, many very stable, very hard minerals have covalent-ionic
bonding.
Jsoc
1-
17 Stem,
col.
K. H. J. CIHm. EAAK.. 1969, f6,
J34
4 londtna Moclela In lnoraonlc Chemlattyl 1 . Jonlc Compound a
Fig. 4.21 Em halpy or
170
decomposition or sulfates
and
as a
funct.ion or size and charge
of the meml cation. [From
Stern, K. H. J. Cllem. Educ.
160
ISO
140
1969, 46, 645-649.
110
Reproduced wilh
permission.]
120
110
'TatOO
E 90
oil 80
...
"'
70
60
so
40
]0
20
0.1
Conclusion
0 .2
0.]
o.s
0.6
0.7
Ionic crystals may be viewed quite simply in terms of an electrostatic model of lattices
of hard-sphere ions of opposing charges. Although conceptually simple. this model is
not completely adequate, and we have seen that modifications must be made in it.
First, the bonding is not completely ionic with compounds ranging from the alkali
halides, for which complete ionicity is a very good approximation, to compounds for
which the assumption of the presence of ions is rather poor. Secondly, the assumption
of a perfect, infinite mathematical lattice with no defects is an oversimplification.
As with all models, the use or the ionic model does not necessorily imply that it is
"true", merely that it is convenient and
and if proper caution is taken and
adjustments are made, it proves to be a fruitful approach.
Problems
4.1
Both CsO and CaF1 exhibit a coordination number or 8 for the cations. What is the
sti'UCiural relationship between these two lanicc.J?
4.2 The contenJS or the unit a:U or any compound must COntain an integral number of
formula units. (Why?) Note that unit cell boundaries uslice" atoms into fraaments: An
atom on a face will be split in lrulf between two cells; one on an ftlge will be split into
quarters among four a:lis, etc. Identify the number of Na and ctions in the unit cell
or sodium chloride illustrated in F"tg. 4.Ja and state how many formula units or NaO the
unit cell contains. Give a complete analysis.
4.3 11le measured density or sodium chloride is 2167 gem- . From your answer to
lem 4.2 and your knowledge of the relationships among density, olume, Avogadro's
Problems
135
number, and formula weight.

the volume of the unit cell and thena: the length
of the edge of ahe cell. Calculate the length r + + r. Chcdt your answer, r + r _, apinsl
values from Table 4.4.
4.4 Study Figs. 4.1-4.3 and convince yourself or the structural relatedness of all or the cubic
structures and of all of the hexagonal slructures.
45 The structure of diamond. a c:ovalena c:rysUll, is shown in Fig. 7.1. How is ia related to
some or the strucaures or ionic compounds discussed in this chaptet'?
4.6
Whal simple mathematical relationship exists be1ween the empirical formula. numbers
of cations and anions in ahe unia cell, and the coordinaaion numbers of the cations and
anions in a binary metal halide, M.X.?
4.7 If you did not do Problem :L21 when you read Chapter 2, do so now.
4.3 One
or the descriptive chemisary of the aransition metals is that the heavier
congenen (e.g., Mo, W) more readily show the highest oxidaaion stale than does the
lightest
(e.g.. Cr). Discuss this in tenns of ionization enetgies.
4.9 Show your understanding or the Bom- Haber cycle by calculating the heat or rormaaion
or potassium fluoride analogous to the one in the text ror sodium chloride.
4.10 Using any
dal.3 from appcopriate sourcei, predict the eruhalpy or fomwion
or KCI by means of a Bom-Haber cycle. You can check your lattice energy against
Table 4.3.
4.11 Usina any nettssarY data from appropriate sources.
or Cas b} means or a Born-Haber cycle.
the enthalpy of foi'INtion
4.12 Show your undersbnding d ahe me:aning or the Maddung COI\Sl:lllt by alculating A
forthe isolated F - ee-F - fragment considered as a purely ionic species.
lose an c:learon and the nonmetal wants to accept an elearon. so the two m.a wilh each other. Criticize !Ius sl.3te
mcnt quantitatively using appropriate abermodynamic quantiaies.
4.13 The ionic bond is often described as "the me1.3l wants to
4.14 Why is the thermile reaction:

!AI+ M,Ol = 2M + AI,Ol IM Fe. Cr. etc.)
(4.29)
so violently exothermic? (The ingredients sl.3n at room

product. iron. etc.. is roltt-n a1 the end of the reaclion.)
nnd the metnl&c
US We have seen. in Clutplcr 2. that plalinum hcxunuoride hM "n electron :111lnity more
than twi<.:e as great as fluorine. Yea when lithium met11l r.:acts wiah plaainum hexafluoride.
the
produca is Li F ", noa Li PaF;. Explain.
4.16 To ionize Mg to Mg:+ C061S twu times as much energy as 10 form Mg. The rormouion
or
is tmJDth.,mic rather than exothermic liS foro -. Nevertheless. magnesium oxide:
is
formulated as Ms'
rather than as Mg
o-
o-
o -.
a.. What theoretical reason can be given for the Mg.. o - rormulation?
b. What simple experiment could be perrormed 10 prove thai magnesium oxide was not
Mgo-?
4.17 Some experimental values of the Born exponent nre: LiF. S.9; LiCI, 8.0: Li8r. 8.7: NaO.
9.1; Na&. 9.5. What is the percent error incurred in the culculntion of IMnice energies
by Eq. 4. 13 when Pauling's 1Cf1eralizalion (He S. Nc 7, etc.) is used instead or ahc
experimental value of n?
4.18 Using Fig. 4_7 aenerate the first five terms of the series ror the Madelung constant for
NaO. How close is thesumm:uion of these terms to the limitina value given in Tablc4_l?
4.19 The enth3Jpy of formation or sodium nuoride is -S71 kJ mol" ' . Estimate the elearon
affinity of fluorine. Compare your val ue with thai given in Table 2.S.
136
M oolola I l lc Choml atry;
t . Ionic
4.28 Calculate the proton allinities of the halide ions. The enthalpics in quesJion an: those o(
x-+H- HX
Compare your val ues with those given in Table 9.S.
4.21 Perform radius ratio calculations to show which alkali halides violate 1hc radius ratio
ruk
I
4.22 Even if there arc exceptions to the radius ratio rule, or if exact data are hard to come by, 1
it is stiU a valid guiding principle. Cite three independent examples of pairs of compounds 1
illustraling structural dilferences resulting from differences in ionic radii.
.
II
4.23 Berkdium is currently available in miaogram quantities-sufficieru 10 dclenninc struolura! parameters but not enough for thermochemical measurements.
a. Using the labulated ionic radii and the radius ratio rule. eslimate the lattice energy
of berkelium dioxide, Blc01 .
b. Assume that the radius ratio rule is violated (it is!). How much di&reoce does this ,
make in your answt:t'?
J
4.24 The crystal suuccure of LaF is different fro m those discussed. Assume iJ is unknown.
Using
equation of K.apustinslcii, estimate the lattice el\Cl"l)'.
4.25 Olpper{l) halides crysW!izc in a zinc blende struclurc. Olpper{ll) ftuoridc crysla]lizcs ill
a dislorted rutile structure (for the putpOSCS of lhls problem assume lhrcre is no
Calcula1e the enthalpies of {ormation of CuF and CuF2 Discuss. (Ail of 1hc necessary
data should be readily ava.ilable, but if you have difficulty finding a quanti1y,
how
much dan argument you can malce without il.)
4.26 Thallium has two SJable oxida1ion S23 res, +I and + 3. Usc the Kapustinslcii equation
to predict the laJtice energies of TIF and TIF , . Predict the enthalpies of formation of
these compounds. Di$CUSS.
4I1 Plot tbe rad.ii of the lanthanide.(Jil) (Ln>+) ions from Table 4.4 versus alomic number.
Discuss.
4.28 AU of the alkaline earth oxides, MO, excepl ooe crystali.ze in lhe roclc salt (NaCI) struc
lure. What is the exception and what is lhe likely structure for it? (Wells, A. F. Srrucrural
l nrx{lllllic Clll!miury, Sth ed.; Oxford Universily. Oxford, 1984.)
4.29 h is n ot difficult 10 show matherruuically that with lhc hard sphere
:JJ!ion- anion
contacl occurs at r /r- 0.414 for C.N. 6. Vet Wells (Siruc.rurul /norganic ClltmislrJ,
5th ed.; Oxford Univcnity: Oxford, 1984) s1a1es tha1even wilh 1he hard sphere
we
should no1 expect lhe change lo lake place until r./r_ == O.JS. Rationalize lhis apparent
coruradiction. (Hint: cr. Fig. 4. 17.)
4.38 'There exists the paliSibilily thai a cenain cfrculurily may develop in the radius ratio
arguments on P'JGC 12S. By assuming a coordination number of 6 were 1he calcula.Jions
biased? Discuss.
4.31 Perform a calculation similar to 1hat on page 127
1he fonnalion of dioxncnyl J
hexaftuoroplatinate(V):
o. + PJF, ---+ OtPJF;
(4..30)
All data (or approximalions, if neoessary) may be obt11ined fi-om Chapters 2 and 4. Predict
the enthalpy of reaction for this equation. CarcfuDy note any assumptions you must
rna lee.
4.32 Rcpe81 the calculation in Problem 4.31, but for tbe n:action:
Xe + P t F , - xePJF;
Should xenon react with platinum hexatluoride?
j
I
(4.31)
Problems
137
4.33 SupPQSC that someone argues wah you that your answer to Problem 4.32 is invalid. and
that any prediction that Neil Bartlett might have made on the basis of similar reasoning
(see Chapter- I 7) is equally invalid4e was just Juclcy- the reaction product of Eq. 01
is not a simple ionic compound. xePtF0, but a mixture of compounds, and apparently
the xenon is covalently bound. What is your reply?
4.34 Calculatethe emhalpyofaherc.actionC\JI21 .,--. Cui.,,+ !I Carefully liSJ any assumptions.
4.35 Which of the foiiOWtng win exhibit the greater polarizing power?
a. K or Ag
b. K or u
d. Cu1+ or Ca1+
e. Ti2 + or y,
c. Li or &>+
4.36 As one progresses across a transition series (e.g.. Sc to Zn) the polarizing power of f>1 1
ions increases perceptibly. In contrast, in the lanthanides, the change in polarizing power
of M' changes much more slowly. Suggest two reasons fo r this difference.
4.37 Some general chemistry textbooks say that if a fluorine atom, Z 9, gains an electron. it
will become a fluoride ion with ten electrons that cannot be bound as tightly (because of
electroJrdectron repulsion) as the nine of the neutral atom, so the radius of the fluoride
ion (tl9 pm) is much greater than the radius of the neutral fluorine atom (7t pm). Discuss
and criticize.
4.38 If the addition of an electron F + e - .... F- causes a greai increase in size. why docs not
the addition of 1wo electrons to fo rm the oxide ion (r_
126 pm) cause it to be much
larger than the fluoride ion (r _ - 119 pm)?
4.39 A single aystal of sodium chloride for an X-ray suuaure determination is a cube 0.3 mm
on a side.
a. Using data from Table 4.4, calculate how many unit cells are contained in this a"YSJal
b. Compute the density of NaCI. Compare your value with that in o handbook.
4.40 There hns been a recent flurry of interest in the possibility of "cold fusion" cJ hydrogen
atoms (the deUierium isotope) in metallic palladium.'" The original idea came from the
enormous solubililyci hydrogen gas in palladium. Palladium metal has an fcc tauice.
Hydrogen atoms occupy the ocJahedral holes. If 70"/. of the octahedral holes are lilted
by hydrogen ntoms and the !:mice does not expand upon hydrogenation. how many
grams of hydrogen will be contained in one cubic oemime1er of the palladium hydride?
Compare this to the density of liquid hydrogen in gcm - 3 Comment. (Rieei<, D: F. J.
Chtm. EJuc. 1989, 66, 1034.)
4.41 Minges and Rolf19 have discussed the packing of molecular ions in terms of their shape
as well as si:ze. Three indices, each ranging in value from 0.00 to 1.00, are used to describe
the shape of an ion: the splltrical ind<x, F,; the cylindrico/ indtx. F,; and the di.scoidol
/ndt.<, F4 Consider the following index values and try to corn:la1e them with what you
know of the shapes of tile ions. If you are uncenain as to the shapes, refer to Chapters 6
and 12.
a. NH:. NMe;. BF;. oo; (TJ), PF;. and

F, 0.00,
; 0.00.
b. Au(CN)i and I.) (D.,.) have values F,
(0) all have values F,
0.00, F,- 1.00. F4
c. AuBr;, PtCI!- (D4J b01h have values F, a 0.00. F,

has values F, 0.00. F, 054, F4 - 1.00.
= O.SO. F4
I .00.
1.00.
1.00, and Ni(CNI!-
d. When il is trigonal bipyramidal (D;1.J,

has values F, 0.75, F, = 0.25,
F1 0.14 but when it is square pyramidal (C..), the values are F,- 0.68, F, = 0.16,
0.32.
"Fltlscl>mann. M.; Poos. S. J. E/ectr0<1110l Ottm. 1989, 261, 301-308.

u Mingos, D. M. P.; Rotc. A. L. lnorg. Clttm. 1991, JO, 3769-377t; J. Clttm. Soc. DIZiU>n 1!191,
3419-3425.
Chop
e r
5
Bonding Models in
Inorganic Chemistry:
2. The Covalent Bond
This chapter and
the one following will be devOted to a preliminary analysis of

covalent bonding. Most of the ideas presented here may be found elsewhere and with
greater rip, and many will have been encOllnterecl in previous courses. However .
since they form the basis for subsequent chapters. a brief presentation is in order here.
Covalent bonding will also be diScussed in Chapters 6 and I I.
The Lewis Structure
This method of thinking about bonding. learned in high school and too often forgotten
in graduate school or before, is a most useful jint
in thinking about molecules.
Before delving into quantum mechanical ideas or even deciding whether moleculnr
orbital or valence bond theory is likely to be more helpful, a Lewis structure should be
sketched. The following is a brief review of the rules for Lewis structures:
I. Normally two
pair up to f orm eath bond. This is a consequence of
the Pauli exclusion principle-two electrons must have paired spins if they are
both to occupy the same region of sp;K:e between the nuclei and thereby attract
both nuclei. The definition of a bond as a shared pair of electrons. however. is
overly restrictive, and we shall see thatJ he early emphasis on electron pairing
in bond formation is
and even misleading.
2. For most atoms there will be u muxim11m of eight

in tire valrnce shell
( = l.Ms
I
This is absolutely necessary for atoms o r the elements lit hium through fluorine since they have only four orbitals (an s and
three p orbitals) in Ihe valence shell. It is quire common, as weD. for atoms of
Other elements to utilize only their s and p orbitals. Under these conditions the
sum of shared pairs (bonds) and unshared pairs (lone pairs) must equal the
number of orbitals-four. T his is Ihe maximum. and for elements having fewer
than four valence electrons, the octet will usually not be filled. The following
comPOllnds illustrate these possibilities:
.. =9:..
:CI:
13 8
:g:H
H
:CI:B:CI:
:CI:
Li :CH 3
Valence Bond Theory
139
3. For
with available d orbitals. the valence shell can bto expanded
beyond an octet. Becnuse d orbitals first appear in the third energy level. they
are low enough in energy to be available for bonding in elements of Period 3
and beyond. These elements are nonmetals in the higher valence compounds
and transition metals in complexes. In the nonmetals, where the number of
valence electrons is usuaby the limiting factor. we have maximum covalencies
of S, 6, 7, and 8 in Groups VA (IS), VIA (16), VIlA ( 17), and VlltA (18).
respectively. Note that covalency (the number of covalent bonds to an atom)
and coordination number (the number of atoms bound to another atom) are not
always the same. Factors determining covalencies and coordination numbers
in complexes are of several kinds, and discussion of them will be deferred.
Examples or molecules and ions containing more than eight electrons in the
valence shell of the central atom are:
F F
I;
F-P
J\
F F
F F
I;
F-S-F
/J
F F
F F F
\II
I-F
/1\
F F F
[ r
'
HJN
I
I I
NH,
Xe
II\
0 0 0
NH 3
4. It has hl'l'n assumed implicitly in all uf these mles that the moleculto will seek
th<' lowest overall ent'rgy. This means that, in general, the maximum number of
bonds will form, lhat the strongest possible bonds will form. ond that the
arrangement of the atoms in the molecule will be such as to minimize adverse
repulsion energies.
Bonding Theory
In modern times there hove been two "contenders for the throne" of bonding theory:
valencto bond theory (VBT) and molecular orbital theory (MOT). The allusion is an apt
one since it seems that much of the history of these two theories consisted of
contention between their reSpective proponents as to which was best. Sometimes
overzealous supponers of one theory have given the
that the other is
"wrong.' Gramed that any theory can be used unwisely. it remains nonetheless a fact
that neither theory should be reg,arded as true to tlu: exclusion of the other. Given u
specific question one theory may prove distinctly superior in insight. ease of calculation, or simplicity and clarity of results. but a different question may reverse the
picture completely. Surely the inorganic chemist who does not beoome thoroughly
familiar with both theories is like the carpenter who refuses to carry a saw because he
already has a hammer! Both are severely limiting their skills by limiting their tools.
Valence Bond
The valence bond (VB) theory grew directly out of the ideas of electron pairing by
Lewis and others. In 1927 W. Heitler and F. London proposed a quamum-mechanical
Jreatment or the hydrogen molecule. Their method has oome to be known as the
valence bond approach and was developed extensively by men such as Linus Pauling
Theory
14 0
S landing Models in lnargonic O.emislry: 2. The Cawal..,l land
and J. C. Slater. The following discussion is adapted from the wortcs of Pauling and
Coulson. I
Suppose we have two isolated hydrogen atoms. We may describe them by the
wave functions 1{111 and o/18 , each having the form given in Chapter 2 for a Is orbital. If
the atoms are sufficiently isolated so that they do not interact, the wave function Cor
the system or two atoms is
(5.1)
where A and B designate the atoms and the numbers and 2 designate elect rons
number I and 2. Now, we know that when the two atoms are brought together to form
a molecule they will affect each other and lhatthe individual wave functions"'" and 1/Ja
will change, but we may assume that Eq. S. l is a good starting place as a !rial function
for the hydrogen molecule and then try to improve it. When we solve for energy as a
function or distance, we lind that the eneray curve for Eq. S. l does indeed have a
minimum (curve o. Fig. 5. 1) of about - 24 kJ mol- 1 at a distance orabout90pm. The
actual observed bond dislallee is 74 pm, which is not too different from our first
approximation, but the experimental bond energy
is -458 kJ mol- 1, almost 20
times greater than our first approximation.
If we examine Eq. 5. 1. we must decide that we have been overly restrictive in
ustng it to descnbe a hydrogen molecule. FII'St, we are not justified in labeling
from each other. Moreover. even if
electrons since all electrons are
we could, we would not be sure that electron I will always be on atom A and electron 2
on atom B. We must alter Eq. S. l in such a way that the artificial restrictions arc
removed. We can do this by adding a second term in which the electrons have changed
positions:
(5.2)
This improvement was suggested by Heitler and London. If we solve for the
energy associated with Eq. S.2, we obtain curve b in Fig. S. l. The energy has
improved gready ( -303 kJ mol - 1) and also the distance h:ls improved slighUy. Since
f ig. 5.1 Theoreticul energy
curves (o-d./) ror the
hydrosen molecule. H2
compared wirh the
experimental curve (e).
Curves a-d show
successive approximations
in the wave function as
discussed in lhe aex1. Curve
f is the
interaction
oltwo electrons of
spin.
200
100
e;
a-roo
...
-200
- )0()
-400
100
t50
200
1!0
tnlmaodtat db...,.,, r (pml
Pailinc. L 1M Na111u if IM Clwmictll IH>ttd, ltd eel; Comd Uni-sily: ltllaca. NY, 1960.
CouiSOft. C.A
2nd eel.: Oxford Univuslty: London. 1961. Mc:Wecny, R. c"""""'
Velkncr; Oxford Univenily: l..ondoa, 1979.
Valence Bond Theory
141
the improvement is a result of our ''allowing" the electrons to exchange places, the
increase in bonding energy is often termed the exchange energy. One should not be
too literal in ascribing this large part of the bonding energy to "exchange," however.
since the lack of exchange in Eq. 5.1 was merely a result of our inaccuracies in
approximating a correct molecular wave function. If a physical picture is desired to
account for the exchange energy. it is probably best to ascribe the lowering of energy
of the molecule to the fact that the electrons now have a larger volume in which to
move. RecaU that the energy of a particle in a box is inversely related to the size of the
box; that is. as the box increases in size. the energy of the panicle is lowered. By
providing two nuclei at a short distance from each other, we have "enlarged the box"
in which the electrons are confined.
A further improvement can be made if we recall that electrons shield each other
(Chapter 2) and that the effective atomic number Z. will be somewhat less than Z. If
we atljust our wave functions, "'"and Y,8 , to account for the shielding from the second
electron. we obtain energy curve c-a further improvement.
Lastly. we must ag;1in correct our molecular wave function for an overrestriction
which we have placed upon it. Although we have allowed the electrons to exchange in
Eq. 5.2, we have demanded that they must exchange simultaneously, that is. that only
one electron can be associated with a given nucleus at a given time. Obviously this is
too restrictive. Although we might suppose that the electrons would tend to avoid
each other because of mutual repulsion and thus tend to stay one on each atom. we
cannot go so far as to say that they will always be in such an arrangement. It is
common to call the arrangement given by Eq. 5.2 the "covalent structure" and 10
consider the inlluence of " ionic structures" on the overall wave function:
H-H ._.... H+H-
--+
H -H+
Jcnc
CoVIllen!
We then write
Y, = .,A(tlf/!8111
Y,AIZIY,Bftl
J.Y,AiliY,A(.!)
(5.3)
where the first two terms represent the covalent structure and the second two terms
represent ionic structures in which both electrons are on atom A or B. Because the
electrons tend to repel each other somewhat. there is a smaller probabilily of finding
them both on the same atom than on different atoms. so the second two Jerms are
weighted somewhat less(),< 1). Equation 5.3 can be expressed more succinctly as
(5.41
When we investigate the energetics of the wave function in Eq. 5.3, we lind further
improvement in energy and distance (curve d. Fig. S.l).
This is the first example we have had of the phenomenon of resonance. which we
shall discuss at some length in the next section. It should be pointed out now.
however, that the hydrogen molecule has one structure which is described by one
wave function, Y,. However, it may be necessary because of our approximations. to
write Y, as a combination of two or more wave functions, each of which only partially
describes the hydrogen molecule. Table 5.l lists values for the energy and equilibrium
distance for the various stages of our approximaJion. together with the experimental
values.
Now, if one wishes. additional "corrections" can be included in our wave
function, to make it more nearly descriptive of the actual situation obtained in the
142
S Bonding Models in lnorg.nic Chemislry: 2.
n.. Covolent Bond
Tobie 5.1
Energies ond ..,<lillrium
distonco& lor VB wove
Nn(tiOftS
Type of wove fundion
Enetgy (lcJ mol- 1)
Di&tonce (pm)
Uncorrected, = t/IAI/Ia
Heitler-Loodon
Addition or shieldina
Addition of ionic contributions
Observed values
24
303
36S
90
86.9
74.3
74.9
74.1
McWccny, R. Coulson's
388
458.0
Oxford
Uneniay: London. 1979: p 120.
Used with permission.
hydrogen molecule.u However , the present simplified treatment has included the
three imponant contributions to bonding: delocalization of electrons over two or more
nuclei, mutual screening, and partial ionic character.
There is an implicit assumption contained in all of the above:
two bonding
are ofopposite spitr. If two electrons arc of parallel spin. no bonding occurs,
but repulsion instead (curve f, Fig. S. l). This is a result of the Pauli exclusion
principle. Because of the necessity for pairing in each bond fonncd, the valence bond
theory is often referred to as t.h e electron pair theory, and it forms a logical quantummechanical extension of lewis's t.h eory of electron pair formation.
Resonance
When using valence bond theory it is often found that more than one acceptable
structure can be drawn for a molecule Of, more precisely, IT10fe than one wave
function cun be written. We have already seen in the case of the hydrogen molecule
that we could formulate il either as H- H or as H + H -. BIXh are acceptable structures, but the second or ionic for m would be considerably higher in energy than the
"covalent" strucaure (because of the
ionization energy and low electron affinity
of hydrogen). However, we may write the wave function for the hydrogen molecule as
a linear combination of the ionic and covalent functions:
(5.5)
where A detennines the contribution of the two wave functions. When this is done. itis
found that the new wave funct ion is lower in energy than either of t he cootribmitrR
structures. This is a case or covalent-ionic resonance which will be discussed aa
greater length in the section on elt.'ctnlltt'l(lllioity.
Another type of resonance arises in the case of ahe carbonuae ion. A simple Lewis
structure suggeSts that the ion should have three u bonds and one 1r bond . However,
when it comes to the placement
the 1r bond. i becomes obvious that there is no
unique way to draw the 1r bond. T here is no a priori reason for choosing one oxygen
atom over the other two to receive the 1r bond. We also lind experimentally that it is
impossible to distinguish one oxygen alQfn as being in any way different rrom the other
two.
or
>A 100-Jenn l"unclion(sec Foouael) hasreprocluccd lhcuperimenaalvalueiO ..OrhinO.OI kJ mot-.

See McWccny. R. Cou/SlJII's Vokn; O>tford Univtnlry: L.lo!don, 1979; pp 120-121, lind Pil>r,
F. L.
QtHJIItWm
McOnw-Hill: New Yon. 1968; "" :z34-.249.
, Kolos. W.; Wobewic:z. L J. Cllnn. Plrys. 1968.
404. See HenbcrJ, G . J. Mol. Sptrosc. 19711.
JJ. 147. for ahc expe.r immlal wlue.
Valence Bond Theory
143
We can draw three equivalent contributinQ suuctures for the carbonate ion:
:Q:
-:R./
II
c
'.u
Ill
Each of these structures may be described by a wave function. 1/11 l/fr 1 or l/fr 11 The
actual structure of the carbonate ion is none of the above, but a rtsonnnct hybrid
formed by a linear combinatioo of the three canonical structurrs:
1/1 = al/fr
b1{111
(5.6)
There is no simple Lewis structure that can be drawn to picture the resooance hybrid,
but the following gives a qualitative idea of the correct structure:
IV
It is found th:lt the energy of IV is lower than that of I, II, or Ill. It is common to
speak of the difference in energy between I and IV as the rtsonance tMrgy of the
carbonate ioo. One should realize. however, that the resonance energy arises only
because our wave functions 1/11, o/111 , o/1111 are rather poOr descriptions of the actual
structure of the ion. In a sense. then, the resonance energy is simply a measure of our
ignoronce of the true wave function. More accurately, the resol!llnce energy and the
entire phenomenoo of resonance are merely t1 result or the overly restrictive approach
in valence bond theory in insisting thnt a "bond" be a loculiuJ puir
we
of electrons between two nuclei. When we encounter a molecule or ion in which one
or more pairs of electrons are dtlotoliud we must t hen remedy the situation by
invoking resonance . We should not conclude, however, that valence bond theory is
wrong-it merely gets cumbersome some times when we have many delocalized
electrons to consider. In contrast, in molecules in which the elect.r ons are localized,
the valence bond theory often proves to be especially useful.
In the carbonate ion. the energies of the three contributing structures are identical. and so aU three contribute equally (a b c) and the hybrid is exactly
intermediate between the three. In many cases, however, the energies of the cootributing structures differ (the hydrogen molecule was an example), and in these cases we
find that the contribution of a canonical structure is invtntly proportional to its
energy. that is. high energy, unstable structures cootribute very little, and for resonance to be appreciable, the energies of the contributing structures must be comparable. Using the energy of the contributing structures as a basis, we can draw up a set of
general rules fur det.cnninif'lg the possibility of contribution or a canooical structure.
144
5 Bonding Models in lnorgo11ic Chemistry: 2. The Covalenl Bond
1. The proposed canonical structure should have a maximum number of bonds,

consistent, of course, with the other rules. In the carbon dioxide molecule, for
example, the structure
:o:c::o:
..: +
plays no appreciable role because of its much higher energy resulting from toss
of the .,. bonding stabilization. In general, application of this rule is simply a
matter of drawing Lewis structures and using good chemical sense in proposing contributing structures.
2. The proposed canonical structures must be consistent with the location of the
atoms in the actual molecule (resonance hybrid). The most obvious consequence of this rule is the elimination of tautomers as possible resonance
structures. Thus the following structures for phosphorous acid represent an
equilibrium between two distinct chemical species, not resonance:
A less obvious result of this criterion is that when contributing structures differ
in bond angle, resonance will be reduced. Consider, for example, the fullowing
hypothetical resonance for nitrous oxide:
n
Aside from the factthatll is a strained structu re and therefore less stable than
I, it will not contribute to the resonance of N20 bec ause the bond angle is 180"
in land 60" in II. For any intermediate hybrid, the contribution of either I or II
would be unfavorable because of the high energy cost when I is bent or when II
is opened up.
A few words should be said about the difference between resonance and
molecular vibrations. Although vibrations take place, they are oscillations
about an equilibrium position determined by the structure of the resonance
hybrid, and they should not be co'l[used with the resonance among the
contributingfonns. The molecule does not " resonate" or "vibrate" from one
canonical structure to another. In this sense the term "resonance" is unfortunate because it has caused unnecessary confusion by invoking a picture of
"vibration." The term arises from a mathematical analogy between the molecule and the classical phenomenon of resonance between coupled pendulums,
or other mechanical systems.
Far the 1110111enllhe dwaes should be icnored: they wiD be cliscussecl;n Rule J as wei as in the ocxt,
Valence Bond Theory
145
3. Distribution of formal charges in a contributing structure must be reasonable.

Formal charge, which will be more fully explained in the next section, may be
defined as the charge an atom in a molecule would have if all of the atoms had
the same electronegativity. Canonical forms in which adjacent like charges
appear will probably be unstable as a result of the electrostatic repulsion. A
structure such as A - -B+ -c+-o- is therefore unlikely to play a major role
in hybrid formation.
In the case of adjacent charges which are not of the same sign, one must
use some chemical discretion in estimating the contribution of a particular
structure. This is best accomplished by examining the respective electronegativities or the a1oms involved. A structure in which a positive charge
resides on an electropositive element and a negative charge resides on an
electronegative element may be quite stable. but the reverse will represent an
unstable structure. For example, in the following two molecules
X
X
'\.
'\.
X-P=O .....- X-P-o/
/
X
X
n
cononical form II contributes very much to the actual structure of phosphoryl

compounds, but contributes much less to B Fl and, indeed, the actual contribution in compounds of this sort is still a matter of some dispute.
Furthermore. placement of adjacent charges of opposite sign will be more
favorable than when these charges are separated. When adjacent. charges of
opposite sign contribute electrostatic energy toward stabilizing a molecule
(similar to that found in ionic compounds), but this is reduced when the
charges are far apart.
4. Contributing forms must have the same number of unpaired electrons. For
molecules of the type discussed previously. structures having unpaired electrons should not be considered since they usually involve loss of a bond
A=B * A - B
II
and higher energy for structure II. We shall see when considering coordination
compounds, however, that complexes of the type MLn (where M = metal,
L = ligand) can exist with varying numbers of unpaired electrons but comparable energies. Nevertheless, resonance between such structures is still
forbidden because the spin of electrons is quantized and a molecule either has
iiS electrons paired or unpaired (an intermediate or .. hybrid .. situation is
impossible).
These rules may be applied to nitrous oxide, N20 . Two structures which
are important are
:N::N::Q: . _ :N:::N:o:
-
+ ...:
II
146
S Bonding Models in Inorganic O.emislry: 2. The Covalent Bond
Both of these structures have four bonds and the charges are reasonably
placed. A third structure
:N:N:::o:
=2 +Ill
is unfavorable because it places a positive charge on the electronegative

oxygen atom and also has adjacent positive charges.
Other possibilities are
:N:N::o:
:N::N:o:
+
tv
and the cyclic structure discussed under Rule 2. This last structure has been
shown above to be unfavorable. Likewise IV and V should be bent and are
energetically unfavorable when forced to be linear to resonate with I and II. In
addition, both have only three bonds instead of four and are therefore less
stable. Furthermore, V has widely separated charges. but they are exactly
opposite to those e?'pectcd from electronegativity considerations.
It is almost impossible to overemphasize the fact that the resonance hybrid is the
only structure which is actually observed and that the canonical forms are merely
constructs which enable us to describe accurately the experimentally observed mole
cute. The analogy is often made that Jhe resonnnce hybrid is like a mule, which is a
genetic hybrid between a horse and a donkey. The mule is a mule and does not
"resonate" back and forth between being a horse and a donkey. It is as though one
were trying to describe a mule to someone who had never seen one before and had
available only photographs of a jackass and a mare. One could then explain that their
offspring. intermediate between them. was a mule.s There is perhaps a better analogy.
though one that will be unfamiliar to those not versed in ancient mythology: Consider
a falcon (a real animal) described as a hybrid of Re (the falcon-headed Egyptian sun
god) and a harpy (a creature with a woman's head and the body Qf a raptor), although
neither of the latter has an independent existence.
Fonnal Charge
In the discussion of several preceding molecules. including nitrous oxide, fomml

charges were assigned without explanation. As we said earlier, formal charge may be
regarded as the charge that an atom in a molecule would have if :111 of the atoms had
the same electronegativity. It may approximate Jhe real ionic clwrge as in the phos
phonium ion, PHt. Phosphorus and hydrogen have
the same elec
tronegativity. The formal charge on each hydrogen atom is :zero and the phosphorus
atom carries a single positive formal charge corresponding to the ionic charge. On the
other hand, some molecules, such as N 20. exhibit formal charges in otherwise neutral
molecules.
:N=N=o:
+
:N=N-0:
+
::
It
'This anaiOSY. like any othc.-. can be pWihed 100 Car. The conJributina structures should not be
considered as "' paretus'" of the hybrid.
Valence Bond
147
In the case of N 20, the electronegativities of nitrogen and oxygen are different. In
boh cases, the calculated formal charges indicate the presence of real electrical
charges on Jhe atomS in question. though not necessarily exactly + I or - I. Spec
ificaUy. the charge density about the two nitrogen atoms is not the same.
To obtain the fomlal charge on an atom, it is assumed that all electrons are shared
equally and that each atom owns" one-half of the electrons it shares with neighbor
ing atoms. The formal charge, QF. is then:
N A - NM
QF
N"- NLP - jN8 p
(5.7)
where N A is the number of electrons in the valence shell in the free atom and NM is the
number of electrons "belonging to the atom in the molecule" ; NLP and N 8 p are the
numbers of electrons in unshared pairs and bonding pairs, respectively.
Applied to the Lewis structure of the phosphonium ion,
.I
or
H-P-H
H
we obtain the following formal charges:
Qp - 5 - 4 = 5 - 0 - HBI =
QH
=I
- I
+I
I - 0 - j(2) = 0
(5.8)
(5.9)
This is in contrast to the ph<Jsplrinl! molecule.

H
or
H-P.-H
for which the formal clwrges are
s-
Q,.
5 - 5 - 2 - J(6) = 0
(S.JO)
QH = I - I - I - 0 - !(2) = 0
(5.11)
To return now to nitrous oxide, N 20, specifically structure I, we have a Lewis

structure:
..
..
:N,::N,::o:
or
N, = N,= O
where 1 = terminal (or left) and c = central, merely as identifying labels. Hence:
QN,
=S-
S - 4 - 1(4)
4 =
s-
- I
QN, =
s-
Q0
6 - 6 = 6 - 4 - i(4) = 0
0 - 1(8) = + I
(5.12)
(5.13)
{5.14)
Likewise, structure II gives a +I charge on N., and - I on the oxygen .

Recently. the concept of fomlal charge has been made more quantifiable by
oombining it with the idea of electronegativity to estimate the relative effects of each in
148
S Bonding Model in Inorganic Chemi11ry: 2. The Cowalenl Bond
determining the total charge QT.61lle equation suggested for determining the charge
on A in the molecule ABn is
(5. 15)
The sum over 8 represents the cumulative elect ronegativity effects buill up over n
bonds in the molecule ABn. When the electronegativities of the bonding atoms are
equal. Eq. S.IS reduces to the simple equation for formal charge, Eq. 5.7. When the
electronegativily difference is large the Ionic character of lhe bond is large , and the
electrons are shifted towards one atom or the othe r. The limit of 2I as XA Xa is 0.
and the electrons have been completely t ransferred from atom A to atom(s) B or,
conversely, when XA Xa 21: is 2, and the electrons have been completely transferred from atom(s) B to atom A. Applied to the N10 molecule. Eq. 5.15 gives
estil113led charges of7
N===N =
-0.33 + 1.10 -0.77

Note that this allocation confirms the + I chJirge on
and splits the: negative charge
between the terminal nitrogen atom and the oxygen atom, with the Iauer getting the
larger fraction because r:A its greater electronegativity.
Although formal charges do not represent real, ionic c harges, they do represent a
tendency for buildup c:l positive and negative charges. For example, consider carbon
monoxide. The only reasonable Lewis structure that maximizes the bonding is the
normal triple-bonded one:
:c:::o:
Note, however, that this places a fonnal positive charge on the oxygen and a formal
negative charge on the carbon. If the electronegativilies of carbon and oxygen were
the same, carbon monoxide would have a sizable dipole moment in the direction
cc:: :o
but since the electronegativily difference llraws elect ron density back from the carbon
atom to the oxygen atom. the effect is canceled and carbon monoxide has a very low
dipole moment, 0.4 x 10- lO C m (0.12 D) .
Hybridization
In the valence bond theOy, hybridization of orbitals is an integral part r:A bond
formation. As we shaU see, the concept need not be explicitly considered in molecular
orbital theory but may be helpful in visualizing the process of bond formation.
Consider the methane molecule, CH. The around state of a carbon atom is JP
corresponding to the electron configuration of lsl2fl2p_!2p} Carbon in this state would
be divalent because only two unp:Ured electrons are available for bonding in the p and
Py orbitals. Although divalent carbon is well known in methylene and carbene intermed"tates in organic chemislly. stable carbon compounds are tetravalent. In order for
four bonds to fonn, the carbon atom must be raised to its l!olence stole. This
A.... L C. J . Am. CIKm. Soc. IJ89, Ill , 9lls-9116.
The charges shown arc averaacs oblainecl by wciFiina resonance saruc:ture ll twke suucture l. See
rcfueoc:e in Foou>ote 6.
Val..,ce Bond Theory
149
the promotion of one of the electrons from the 2s orbital to the formerly empty 2p
orbital. This excited ss state has an electron configuration
This
promotion costs 406 kJ mol-t. Because the valence state, V4 , is delined as the state of
an atom in a molecule, but without the addition of bonded atoms, it is necessary to
supply a further amount of energy to randomize the spins of the 'S state, that is. to
supply enough energy to overcome the normal tendency toward parallel spins.s
Despite all of the energy necessary to reach the valence state, the formation of two
additional bonds rnalces CH 4 895 kJ mort more stable than CH2 + 2H.
Hybridization consists of mixing or linear combination of the "pure" atomic
orbitals in such a way as to form new hybrid orbitals. Thus we say that the single 2s
orbital plus the three 2p orbitals of the carbon atom have combined to form a set of
four spatiaUy and energetically equivalent sp3 hybrid orbitals. This is illustrated in
Fig. 5.2 for the conceptually simpler case of the sp hybrid formed from an s orbital and
a single p orbital. Combination of the s and p orbitals causes a reinforcement in the
region in which the signs of the wave function are the same, cancellation where the
signs are owosite.
If we let t/Js and t/Jp represent the wave functions of an sand a p orbital, then we
combine them to make two equivalent orbitals as follows:
t/Jdl,
= v1 (t/1, +
"'tfl.: =
t/Jp)
(5.16)
Vl(t/1.- t/Jp)
(5.17)
where v1 is the normalizing coefficient and t/JJ1, and t/Jdi1 are the new digonnl (dt) or sp
orbitals.
MathematicaUy, the formation of spl or tetrahedral orbitals for methane is more
complicated but not basically different. The results are four equivalent hybrid orbitals.
each containing one part s to three parts p in each wave function, directed to the
corners of a tetrahedron. As in the case of sp hybrids, the hybridization of s and p has
Fig. 5.2 Formation of sp
hybrid orbitals by the

addition and subtraCtion c:J
anaul..- wave functions.
The exis.tenc.e of thi$ extra .alcnce $l.aiC excitation enc:ray may be clearu if the re-cne process is
considered. If (in a thouahl experimeru) four hydrogen otorns are removed from methane but the
carbon le not alowed to chana in any way, the resultina spins woukl be perfecUy randomitcd.
Energy would !ben be released if the spins were allowed to become paralic:!. See McWeeny. R.
Coulson's
Oxford University: London. 1979; pp ISO. 201-203,208-209. h should be noted
that unlike lP, s. esc., V4 is not an observable spectroac:opic elate buc is c:alcutated by addina
promotion enefiies related lo the electron spine.
150
S Bonding Mode ls in Inorganic Chemistry: 2. The Co.,olfll Bond
Fig. 5.3 Elecuon density

COnlours for an sp> hybrid
orbital. Nme that the nodal
surfucc docs not pass
throuah the nucleus.
resulted in one lobe of the hybrid Ol'bital being much larger than the other (see
FtS. 5.3). Hybrid orbilals may be pictured in many ways: by several contour surfaces
(rag. 5.3); a single. outer contour surface (Fig. 5.4a); cloud pictures (Fig. 5.4b); or by
simpler, diagrammatic sketches which ignore the small lobe ofthe orbital and picture
the larger lobe (rtS. 5.4c). The laner, thou&h badly distorted. are commonly used in
drawing molecules oootainin.: seveml hybrid orbitals.
It is possible to form a third type of s-p hybrid containirag one s Ol'bital and lwo p
orbitals. This is called an spl or trigonal (tr) hybrid. It consists of three identical
orbitals, each of which does not differ appreciably in shape from Fig. 5.3 and is
directed toward the corner of an equilaternltriangle. The angles between the axes of
the orbitals in a trigonal hybrid are thus all 120".
Although promotion and hybridization are connected in the formation of methane
from carbon and hydrogen, care should be taken 10 distinguish between them. Promotion involves the addition of energy 10 raise an electron to a higher energy level in
order that the two additional bonds may form. II is oooceivable thai after promotion
the carbon atom could have formed three bonds with the three p orbitals and the
fourth with the s orbital. That carbon forms tetrahedral bonds instead is a conse-
<J
Of
C)
Cal
C<l
Fig. 5.4 Other ways of

hybrid Olbilllls: (a) orbital shape shown by a sin&le
eoniOUr, (b) cloud rcpreseNation, (c) simplified
The small beck lobes have
been omitted and the shape streamlined to make il easier to draw
conlaini,.
several bybrid orbitals.
Volence Bond n..ory
151
que nee of the greater stability of the latter. not a necessary result of promotion. Thus.
although promotion and hybridization often occur together. either could occur without
the other.
A second point to be made with regard to hybrids is the source of the driving force
resulting in hybridization. Statements are often made to the effect that "methane is
tetrahedral because the carbon is hybridized sp'." nus is very loose usage and gets
the cart before the horse. The methane molecule is tetrahedral because the energy of
the molecule is lowest in that configuration, principaDy because of increased bond
energies and decreased repulsion energies. For this molecule to be tetrahedral, VB
theory demands that spl hybridization take place. Thus it is incorrect to attribute the
shape of a molecule to hybridization-the latter prohibits certain configurations and
c1llvws others but does not indicate a preferred one. For example, consider the
following possibilities for the methane molecule:
H%- -f
H\ /H
t80"
H
120'
II SfJ 1 +tJ
tstJ 3
.J;
-125"
lltsp +t'1
IV s +p 3
The first three geometries involve the tetrahedral, trigonal. and digonal hybrids
discussed above and the fourth involves the use of pure s and p orbitals 11s discussed
on page 149. The last s tructure contains three equivalent bonds at mutual angles or 6fJ'
and a fourth bond at an angle of approximately 145 to the others. It is impossible to
construct s-p hybrid orbitals with angles less than 90", and so structure V is ruled out.
In this sense it may be said that hybridization does not "allow" structure V. but it may
not be said that it "chooses" one of the others. Carbon hybridizes sp, spz, and spl in
various compounds. and the choice of sp3 in methane is a result of the fact that the
tetrahedral structure is the most stable possible.
Although we shall not mDke explicit use of them. the re11der may be interested in
the form of the s-p hybrids we have scen.9
(5. 1g)
.,,, = Vf "' +
.,,!
Vfo/1,, - Yff/1,, +
tit,,= Vftlt, - Vftlt,, .,,., = lo/1. + lo/1,., + 11/1,_
.,,... = lo/1, - lo/1,., - lo/IP.<.,,.. = ltlt, + lo/1,, - lo/1,,
=
"'" =
Yfofi,.,
(5.19)
(5.20)
+ ltlt,.
(5.21)
+ lo/1,,
(5.22)
- lofi,.
(5.23)
lo/1, - lo/1,, + 11/!P.-- - lo/1,,
(5.24)
The percent sand p Charac1er iJ proponionalto t he squares oC the coeJI\Qems. Taken Crom Hsu.
C. Y.; Orchin, M. J. Clu!m. EJuc. 1m. SO, 114-118.
152
5 l anding Mo dels in Inorganic Chemiolry: 2. lM Cowolenl Bond
Table 5.2
Bond ongleo of hwbrid
...toiloil
Sp (di)
spl (tr)
sp'J (tel
dspJ
Linear (digonal)
Trigonal
Tetrahedral
Trigonal bip)'nlmidal or
Square pyramidal
Octahedral
BCIIICI angle[)
180"
120"
109!"
900, 120"
>900,<900
900
It is not necessary to limit hybridization to s and p orbitals. The criteria are that
the wave functions of the orbitals being hybridized must be of appropriate symmetry
(Chapter 3) and be similar in energy . If the orbitals are not close in energy , the wave
function of the hybrid will be unsuit.ed for bonding because !he electron density would
be spread too thinly. In practice this means that hybrids are formed among orbitals
lying in the same principal energy level or, occll5ionally, in a<ljacent energy levels.
Some hybrid orbitals containing s. p, and d orbitals are listed in Table S.2. The
structural aspects of various hybrid OC'bit.als will be discussed in Chapter 6, but the
bond angles between orbilals of a given hybridization are also listed in Table 5.2 for
reference.
Most sets of hybrid orbitals are equivalent and symmet ric, that is. four spl orbitals
directed to the comers of a regular tetrahedron. six tfls pl orbitals 10 t.he caners of an
octahedron, etc. In the case of spld hybrids the resulting orbicals are not equivalent. In
the triplal bipyramidal arrangement three orbitals directed trigonally form one set cl
equivalent orbitals (these may be considered spl hybrids) and two orbitals directed
linearly (and perpendicular to the plane of the first three) form a second set of two
(these may be considered dp hybrids). The former set is known as the equatorial
orbitals and the latter as the axial orbitals. Because of the nature of the different
orbitals involved, bonds formed from the two are intrinsically different and will have
different properties even when bonded to identical atoms. For example. in molecules
like PF, bond lengths differ for axial and equatorial bonds (sec Chapter 6).
Even in the case of s-p orbitals it is not necessary that all the orbitals be
equivalent. Consider the water molecule. in which the H- 0-H angle is 1041".
which docs not correspond to any of the hybrids described above, but lies between the
1091" angle for spl and 900 for pure p orbitals. Presumably the two bonding orbitals in
water are approximately tetrahedral orbitals but contain a little more p character,
which correlates with the tendency of the bond angle to diminish toward the 900 of
pure p orbitals. The driving forces for t his effect will be discussed in Chapter 6.
The relationship between p or s character and bond angle will also be discussed in
Chapter 6. For now we need only consider the pOSSibility of s-p hybridization other
than sp, spl, and spJ. If we take the ratio of the s contribution to the IOta! orbital
complement in these hybrids, we obtain SO%, 33%, and 25% :s character, respectively,
for these hybrids. A pure s orbital would be 100"-' s. and a p orbital would have O"j. s
character. Since hybrid orbitals are constructed as Linear oombinations of s and p
orbital wave functions,
(5.25)
there is no constraint that a and b must have values such t.h al the :s character is exactly
25%. 33%. or SO"/.. A value of 20% s character is quite acceptable, for example, and
---
Molecular Orbital Theory
Effect of hybridixotioft on
.,_top and bond
H-:C:;=C--:H _
H1C=CHz. .
CH4
Sp
sp1.
sp3
-p
C-Hbond""""!JY
(kJ mol-l)
C-Hbond
length (pm)
500
410
106.1.
108.6
109.3
33S
112.0
400
153
McWeeny, R. Coubtm;.r Yoknu; Oxford Uni..ersny: London. 1979; p 204.
indeed this happens to be the value in water. When the hybridization is defined as
above,the% p character is always the complement of%s. in the case of water, 80"/..
Hybridization
and Overlap
We may make the generalization that the strength of a bond will be roughly proportional to the extent of overlap of the atomic orbitals. Both pure s and pure p orbitals
provide relatively inefficient overlap compared with that of hybrid orbitals. The
relative overlap of hybrid orbitals decreases in the order sp > spl > spl >> p . The
differences in bonding resulting from hybridization effects on overlap can be seen in
Table 5.3. The C-H bond in acetylene is shorter and
than in hydrocarbons
having less s character in the bonding orbital. The hybridization in the hydrocarbons
listed in Table 5.3 is dictated by the stoichiometry and stereochemistry. In molecules
where variable hybridization is possible. various poSsible hybridizations. overlaps,
and bond strengths are possible. Other things being equal , we should expect molecules
to maximize bond energies through the use of appropriate hybridizations.
Molecula r O rbital
A second approach to bonding in molecules is known as the molecular orbital (MOl

theory. The assumption here is that if two nuclei are positioned at an equilibrium
distance, and electrons are added, they will go into molecular orbitals that are in many
ways analogous 10 the atomic orbitals discussed in Chapter 2. In the atom there ares,
p, d. J. . .. orbitals determined by various sets of quantum numbers and in the
molecule we have u, " S . . orbitals detemlined by quantum numbers. We should
expect to find the Pauli exclusion principle and Hund's principle of maximum multiplicity obeyed in these molecular orbitals as well as in the atomic orbitals.
When we attempt to solve the SchrOdinger equation to obtain the various molecular orbitals. we run into the same problem found earlier for atoms heavier than
hydrogen. We are unable to solve the SchrOdinger equation exactly and therefore
must make some approximations concerning the form or the wave !'unctions for the
molecular orbitals.
Of the various methods of approximating the correct molecular orbitals, we shall
discuss only one: the linear combination of atomic orbitals (LCAOJ method. We
assume that we can approximate the correct molecular orbitals by combining the
atomic orbitals of the atoms that fom1 the molecule. The rationale is that most of the
time the electroos will be nearer and hence .. controlled.. by one or the other of the two
nuclei, and when this is so, the molecular orbital should be very nearly the same as the
atomic orbital for that atom. The basic process is the same as the one we employed in
constructing hybrid atomic orbitals except that now we are combining orbitals on
different atoms to form new orbitals that are associated with the entire molecule. We
Theory
154
5 Bonding Models in Inorganic O.e...iury: :Z. Tlte Cowalenl Bond
therefore combine the atomic Ofbitals t/111 and l/lo on atoms A and B to obtain two
molecular orbimls: to
(5.26)
1/ib = 1/111 + t/lo
(5.27)
"'" = 1/111- l/lo
The one-electron molecular orbitals thus fonned consist of a bonding molecular

orbillll (I/IJ and an ontibonding molecular Ofbital (1/111). If we allow a single electron to
occupy the bonding molecular Ofbillll (as in
for example), the approximate wave
function for the molecule is
H;.
(5.28)
For a tw(H:Iectron system such as H1 the total wave function is the product of the
wave func.tions for each electron:
1/1
t/lblut/16!21 - ll/lllnl +
rJt o/IMIII/J/1111
(5.29)
+ tlooml
+ 1/18(111/JIIIll + 1/JIIwr/111111 + 1/JAtllr/18111
(5.30)
The results for the MO treatment are similar to those obtained by VB theory. Equation
s..30 is the same (when rearranged) as Eq. S.J except that the ionic terms
and \1-81111/11111,) are weighted as heavily as the covalent ones (1/1,.1111/io121 and \I<N 211/io111l.
This is not surprising, since we did not talce into account the repulsion of electrons in
obtaining Eq . S.29. This is a general result: Simple molecular orbitals obl3ined in this
way from the linear combination of atomic orbitals (LCAO-MO theory) tend to
the ionicity of molecules. and the chief problem in adjusting this simple
method to make the results more realistic consists of taking into accounl f!lectron
correlation. As in the case of VB theory it is pOSsible to optimi:tc the wave function by
the addition of correctins terms. Some typical results for the hydrogen molecule arc
listed in Table S.4.
The two orbi11ls 1/Jh and 1/1., differ from each other as follows. In the bonding
molecular orbital the wave functions for the component atoms reinforce each other in
the region between the nuclei (Fig. S.Sa, b), but in I he antibonding molecular orbital
they cancel. forming a node between lhe nuclei (Fig. S.Sd). We are, of course,
Toble 5.4
-gies ond equilibrium
di>lancos for MO w.,.,.
"-'iom ift H2
Energy (kJ mol- l)
Type of wave lvnc1lon

Uncorrected, lit 1/111
Addition of shielding
MO,SCFiimit
Observed values
+ t/lo
Mc:Weeny, R. Cculson'.t
p 120.
wilh petntWion.
260
337
349
4S8.0
Olll'onl Univcnil)':
8S
73
74
.. 74.1
1979;
Mole cui Orbital Theory
155
Cal
lbt
Ccl
Ah
A
!d)
let
Fig. 5.5 (a) "'"' aJ1d <Ita ror individual hydrogen atoms (cr. F"t t. 2. 1). Ib) <It .. "'"' + ..,.
(c) Probabilily funaion for the bonding orbital,
(d) <it.. "'"' - <Itt. (e) Probability
runction r...- the arniborldinc olbilal. 4f.. N01e I hal the bonding orbilal increases the eleclron
density between the nuclei (c) , bUi that 1he anlibottding orbital decreases electron densicy
between 1he nuclei (e).
interested in learning of the elcctron distribution in the hydrosen molecule, :tnd will
therefore be interested in the sq11arl! of the wave functions;
1/1!, + 2!/JAo/JB +
(5.31)
o/J! = o/Ji - 2!/J,.o/Ja +
(5.32)
The difference between the 1wo probability functions lies in the cross term 2!/JAo/Ja- The
integral Jo/J,.tlt8tfris known the ovmop integrol. S. and is very important in bonding
theory. In t.he bonding orbital the ovet1ap is positive and the electron density between
the nuclei is incuased, whereas in the antibooding orbital the electron density be
tween the nuclei is decreasrd. (See Fig. S.Sc, e.) In the former C3Se the nuclei are
shielded from each other and the attraction of both nuclei for the electrons is enhanced. This results in a
of t he energy of the molecule and is
a
bonding situation. In the second case the nuclei are p:ll'tially bared toward each other
and the dectrons tend to be in those regions of
in which mutual attraction by
156
SBonding Models in Inorganic Chemistry: 2. The Covalenl Bond
both nuclei is severely reduced. This is a repulsive, or antibonJing. situation. An

electron density map ror the hydrogen molecule ion, H;. is shown in rrg. 5.6 illustrating the differences in electron densities between the bonding and antibonding
conditions. 11
We have postponed nonnalization or the molecular orbitals until now. Because
f 1/!Ztfr = I for the probability of finding an electron somewhere in space.lhe i.ntegral or
Eq. 5.31 becomes
+ 2JI/IAI/IadT]
where N his the nvrmali;;ing constant. If we let S be the overlap integral, f 1/1A
have
2s]
Now since the atomic wave functions

and f 1/1
each equal one. Hence
(5.33)
we
(5.34)
!/lA and 1/fs were previously normalized,
(5.35)
(5.36)
and
(5.37)
For most simple calculntions the value of the overlap integral. S, is numericaUy rather
small and may
be neglected without incurring too great an error . This simplifies
,..
(b)
Fig. 5.6 Electron densily contours for the H! ion: bondina (a) and antibondina (b) orbit:lls.
II The eltCII'ondensily map ise:uiertooblainforH! than for H1 because it isn01 necessary to comet
for electron lntcnctiOil$. The differences are nol areac.
Moleculo Orl>ilcol TMory
1 '!iT
the algebra considerably :md is sufficiently accurate for most purposes. Wit h complete
neglect of overlap, our molecular wave functions become
1/Jh
v'f(t/JA + 1/Js)
(5.38)
"'
v'f(l/JA - 1/Ja)
(5.39)
The idea of "complete neelect of overlap" refers only to the omission of 1he
matlematical value of the overlap integral in the no rmalization calculation. Note.
however, that " good overlap" in the qualitative sense is necessary for good bonding
because the covalent energy,
is proportional to the extent that the atomic orl>itals
overlap. If o verlap is neglected in the c-.llculotions. the stabilization and destabilization
of bonding and anlibonding orbitals are equal (Fig. S.7). and the value for both
normalizalion constanls is (Eqs . S.36 and S.37) N., N 0.71. If the overlap is
explicitly included in the calculations. the normalization coefficients are N, = 1.1 1
and Nb = 0.56. Olhcr molecules have smaller o verlap integrals lhan H2 and so lhe
effect is less.
As we have seen from Eqs. S.J I and S.32 Jhe only difference between the electron
distribution in the bonding and antibonding molecular orl>itals and the atomic ori>itals
is in those regions of space for which both t/1A and t/le have appreciable values, so that
their product (S .. 11/fA t/fad'rl has an appreciable nonzero value. Furthermore. for
bonding, S > 0, and for antibonding, S < 0. The conditionS = 0 is termed nonbollding
and correspOO<Is to no interaction between the ori>itals. That S serves as a criterion for
bonding. antibonding, and nonbonding conditions is consistent with our earlier assertion that bond strength depends on I he degree of overlap of atomic orl>itals. In general,
we should expect that bonds will form in such a way as to maximize overlap.
In s orbitals the sign of the wave 1\lnction is everywhere the same (with the
exception of small, intranodal regions for n > 1). and so there is no problem with
matching the sign of the wave functions to achieve positive overlap. With p and d
orbitals. however, there arc several possible ways of arranging t he orl>itals, some
resulting in positive overlap, some in negative overlap. and some in which the overlap
is exactly zero (Fig. S.8). Bonding can toke place only when the overlap is positive.
. .A-+-<
61.",
t..
I
\
'
'
!.....
00
>--+--.. .
Fig. 5 .7 EUrgy levels for the H2 molecule wi1h neglec1 of overlap. The quantily ll..
the difference in cnc:r&Y between the energy levels of the
moms ;mel the
hooding molecular orbil.al. II is equal to 4SilltJ mot- .
a Only a
minimum or sym""'uy R included in lhis aud the followina uaion. and to undcrSWIter and io followina cbplen.
158
5 Bonding Models in Inorganic Chemistry: 2. The Covolent Bond
S>O
S<O
(I)
(J)
(b)
(h)
_____fOOl_
(cl
til
Id)
(j)
--w
_S:f1j_
_S:f1j_
lkl
(c)
(I)
"
(m)
ll)
SO
y
(n)
(0)
Fig. 5.8 Arransemeru of alomic orbilals resultina in positive (a-o. negative (g-1). and :r.ero
(m-o) overlap.
Molecular Orbilal Th.oory
159
It may occur to the reader that it is always possible to bring the orbitals together in
such a way that the overlap is positive. For example, in Fig. S.Sg, h if negative overlap
is obtained, one need only invert one of the atoms to achieve positive overlap. This is
true for diatomic molecules or even for polyatomic linear molecules. However, when
we come to cyclic compounds, we no longer have the freedom arbitrarily to invert
atoms to obtain proper overlap matches. One example will suffice to illustrate this.
There is a large class of compounds of formula (PNX1 )n (X
F, 0, Br),
containing the phosphazene ring system (see Chapter 16). The trimer, PlNl X6 , is
illustrated in Fig. 5.9. Note the resemblance to benzene in the alternating single and
double bonds. Like benzene. the phosphazene ring is aromatic. that is, the 1r electrons
are delocalized over a conjugated system with resonance stabilization. The description
of the " bonding in the phosphazene ring, which involves p orbitals on the nitrogen
atpms and d orbitals on the phosphorus atoms, has been a rnalter of considerable
debate. One view is illustrated in Fig. 5. 10, in which the phosphazene ring has been
split open and arranged linearly for clarity. We start on nitrogen atom number one (N 1)
and assume an arbitrary assignment of the positive and negative lobes of the p orbital.
The phosphorus atom 1r bonds through its d orbitals, and so for the P1 atom we draw a
Fig. 5.9 Comparison of
bondina in the rina systems
of (a) ben1ene aDd (b)
hexachlorotriphosphazene.
,.,
fl>)
c,
c.
c,
c.
c,
c.
c;
(bl
Fig. 5.10 Overlap of the ortitllls in the p-p ., system in benzene (a) and the p-d ,. sys.tem in
the phosphazene ril18 (b). Nae the mismatch of ortil31 symmetry in the Iauer.
160
SBonding Modela in lnorvanic Chemistry: 2. The CoyaJeal Bond
d orbital with appropriate symmetry such that the overlap between Nt and P 1 is
greater than zero. We continue with N 2 , P1 , N 1 , and P1 , each time matching the orbital
symmetries to achieve positive overlap. However, when we come to Jhe overlap
between p 3 and Nt (to close the ring) we find that we would like to have the N 1 orbital
lie as shown on the right, but we have previously assigned it the arrangement shown
on the left. It is impossible to draw the six orbitals in such a way as to avoid a
mismatch or node in the system.
Symmetry of
Molecular Orbitals
Some of the possible combinations of atomic orbitals are shown in Fig. 5.11. Those
orbitals which are cylindrically symmetrical about the internuclear axis are called
a orbitals, analogous to an s orbital, the atomic orbital of highest symmetry. If the
internuclear axis lies in a nodal plane, a 1r bond results . In 6 bonds (Chapter 16) the
internuclear axis lies in two mu1ual!y perpendicular nodal planes. AD antibonding
orbitals (identified with an ) possess an additional nodal plane perpendicular to the
internuclear axis and lying between the nuclei. In addition, the molecular orbitals may
or may not have a center of symmetry. Of particular interest in this regard are TTP-1'
orbitals, which are ungerade, and
orbitals, which are gerade.
w;...,
Molecular Orbitals
in Homanucleor
Diatomic Molecules
Molecules containing two atoms of the same element are the simplest molecules to
discuss. We have already seen the results for the hydrogen molecule (page 157;
Fig. 5.7) and for the linear combination of sand p orbitals (Fig. 5.8). We shall now
investigate the general case for molecular orbitals formed from two atoms having
atomic orbilals Is, 2s. 2p. 3s, etc.
There are two criteria that must be met for the formation of bonding molecular
orbitals. Jhat is. orbitals that are more stable (lower in energy) than the contributing
atomic orbitals. One is that the overlap between the atomic orbitals must be positive.
Furthermore, in order that there be effective interaction between orbitals on different
atoms. the energies of the atomic orbitals must be approximately the same. For now
we will assume that molecular orbitals will ronn from corresponding orbitals on the
two atoms (i.e.. Is + Is, 2s + 2s. etc.). We shall soon see that under some
circumstances this assumption will have to be modified. When we combine the atomic
orbitals in this way. the energy levels shown in Fig. 5. 12 are obtained. The :lppropriate
combinations are: IJ
u,.
= lsA
ur, =
u-u
0'1p
Iss
lsA - Iss
2sA
ot =
+
+
2ss
2sA - 2se
'"lp, 'lrlp,
2pyA
= 2PxA
+
+
2pyU
2pxS
?tt,_ =
2PyA - 2py8
11t,,
2pxA - 2px8
= 2pzA + 2p.s
= 2p,A - 2P:s
u,. ur.
The
and
orbitals correspond to the molecular orbitals seen previously for the
hydrogen molecule. The atomic 2s orbitals form a similar set of u and a* orbitals. The
"Symbols A and 8 rcpl"e$Cnl

'Y
rcpre5em orienWion of the p O<biJals. No1e tll&l the
"lllomic ortJitaJ labels" (e.g.. Is) con llf'piY only to molecular orbitals coiU.lructed by mixina two
orbilals or the same type. We shall see later (pqe 164) that tbis is "!' oversimplification.
Moleetllot' O rbilal Theory
00
0-0
+
(I
161
a, or'\-
Cbl
0: . . !0
I
o, oto1
(C)
(d)
0
0
----00
0
- --0
00
p
i'liQ
1GGI
00-00
I
I
a;
I:
I
(e)
co
Fig. 5.11 Symmetry of molecular orbilals formed from acomic orbicnls
cr (a-d)
and ., (e. f) orbicals. and bondina (a, c, e) and llnlibondina (b, d, () orbitllls. The orbitals are
depicted by elearon deflsicy skecches with che sian of t/1 superimposed .
atomic p orbitals can ronn u bonds rrom direct ("head on") overlap or the p, orbitals
and two,. bonds from parallel overtap or the Py and orbitals. Because the overlap is
greater in the former case, we should expect the covalent energy to be greater also
(page 153), and u bonds arc generally stronger than w bonds. Hence the uz, orbital is
stabilized Oowered in energy) more t han the ,.z, orbitals, and conversely the corresponding anti bonding orbitals are raised aec:ordingfy. By analogy with atomic electron
configurations, we can write molecular electron configurations. For H 2 we have
H2 =
ul11
162
5 Bonding Models in Inorganic Chemnh'y: 2. The Covolent Bond
o,
Fig. 5.12 Simpllfied

molc<:ular olt>ital energy
levels for diatomic
molecules of elements in
me second period.
assuming no mixing of s
IU1d p ortitals. The three 2p
Olbilnls are deaenerate. that
is. they all have the same
energy and might also be
as-- -.
shown
The moleCUle shown is
dioxysen.
Using Fig. S. l2 as a guide, we can proceed to build up various diatomic molecules

in much the same way as the aujbau principle was used to build up atoms.
I. Molecules containing one to four t>lt>ctrons. We have already seen the H!
molecule in which there are two electrons in the ua. orbital. Two bonding
electrons constitute a chemical bond . The molecular orbilal theory does not
restrict itself to even numbers of bonding electrons, and so the bond order is
given as one-half the difference between Ihe number of bonding electrons and
the number of antibonding electrons:
(5.40)
is unknown since the number of antibonding electrons

(2) is equal to the number of bonding electrons (2) and the net bond order is
zero . With no bond energyt to overcome the dispersive tendencies of entropy,
two helium atoms in a "molecule.. wiD not remain together but lly apart. If it
existed, molecular helium would have the electron configuration:
The molecule
He2
14
ActuaDy, if the alculation n made can:(uly. lhe bond energy of He 1 is posiriw. If overlap is noJ
nqlected in the calculation. the lnli>ondin& ortital is mort cleslabilizina than the bondirc orbital is
and so He1 has a repulsive encr&Y forcin& it apan. This is another upecJ or the Pauli
S1al>ilizj113.
principle...,.wo electrons of the same spin cannot occupy the same reaion of space.
Mol.c:ular O.t.ital Theory
1 63
If helium is ionized. it is possible to form diatomic helium molecule-ions,

Such a molecule will contain three electrons. two bonding and one
antibonding, for a net bond order of one-half. Such a species. although held
together with only about one-half the bonding energy of the hydrogen molecule, should be expected to exist. In fact it does, and it has been observed
spectroscopically in highly energetic situations sufficient to ionize the helium.
That it is 110( found under more familiar chemical situations as, for example, in
salts, He:;x-. is not a result of any unusual weakness in the He-He bond,
but because contact with just about any subsUinCC will supply the missing
fourth electron with resultant conversion into helium atoms.
lsoelectronic in a formal sense. but quite different in the energies involved
i:s the xe; ion believed' to exist in certqin very acidic solvents (see Chapter 17).
The energetics of the situation are not completely understood, but presumably
the much lower ionization energy of xenon can more readily be compensated
by the solv&ion energy of the polar solvent, thus smbilizing the xe; cation.
2. Lithium and bc-ryl/iwm . Two lithium atoms contain six electrons. Four will fill
the ub and ar. orbitals with no bonding. The last two electrons wiU enter the
ub orbital. giving a net bond order of one in the 4 molecule. The eleciTon
will be
=
where K stands for the K (Is) shell.''

Eight electrons from two beryllium lltoms fill the four lowest energy levels.
u:!<.
a net bond order of zero, as in
with an electron
configurlllion of:
at.
=
KKu!,
Lilc.e the dihelium molecule,

is not expected to exist. The experimental
facts are that lithium is diatomic in the gas phase but beryllium is monatomic.
l . Oxygen, fltmrine. and rwun. These three molecules can be treated with the
same energy diagram that we have been using for other diatomic molecules c:K
the second-row elements. As we shall see shortly, the inlervening molecules,
B C and N require additional considerations. which lead to an alteratiOn in
the rclative energies of the molecular orbitals.
The oxygen molecule was om: of the lir.ll applicutions of molecular orbital
theory in which it proved more successful than valence bond theory. The
molecule contllins si11tccn electrons. Four of these lie in the Ut. and o1.
orbiUIIs, which cancel each other and may thus be ignored. The next four
electrons occupy ab and ui, orbitals and also contribute nothing to the net
bonding. The remaining eight electrons occupy the uZp, 1T2p and 1r;P levels
giving as the electron configuration:
02 =
However. examination of the energy level diagram in Fig. 5. 12 indicates that
the 1r;,. level is doubly degenerate from the two equivalent 1r orbitals,
and
u Tho inner sr..s or care dcarona arc ollen llbbrcvlaled since no net bondina 1:1kes place in lhcm.
1bc symbols used. K. 1., M, oc:.. relet 10 the older I)ISiem or deslcna>iiC the principal """'IY
levels. n
I (K)." 2 (L). etc:. Tbus Na, KK LL
tr,,t.
164
S Bondig Models in Inorganic Ch-islry: 2. The Covalent Bond
v;.,,.
Hund's rule of maximum multiplicity predicts t hat the two electrons

entering the ..- level wiU occupy two different orbitals. so the electronic
configuration can be written more explicitly as
02
.,.;!,
This has no effect on the bond order, which is still two [!(6 - 2)], as
anticipated by valence bond theory. The difference lies in the paramagnetism
of molecular oxygen resulting from the two unpaired electrons. (In this regard
0 2 is analogous to atomic carbon in which the last two eleclrons remained
unpaired by entering different, degenerate orbitals.) The simple valence bond
theory predicts that all electrons in
will be paired; in fact, the formation
of two bonds demands that the maximum number of electrons be paired. This
is the first case of several we shall encounter in which the stress placed on
paired bonding electrons is exaggerated by the valence bond theory. The
molecular orbital theory does not require such pairing as it merely counts the
number of bonding versus antibonding electrons. The experimentally measured paramagnetism of 0 2 confinns the accuracy of the MO treatment .
For the fluorine molecule, there will be a total of 18 electrons distributed:
F2 =
The net bond order is one, corresponding to the u bond, and agreeing with the
valence bond picture.
The addition of two more electrons to form the Ne 2 molecule will result in
filling the last anl ibondi.ng orbital. the ut, orbital. This will reduce the bond
order to zero and Nf:t, like He2 , will not exist.
4. Boron. carbon, and nitrogen. According to Fig. 5. 12, the 8 2 molecule would
be predicted to have a single u bond and be diamagnetic. Experimentally the
8z molecule is found to have two unpaired electrons. The C. molecule would
be predicted to have an electron configuration
and be
paramagnetic. The experimental evidence indicates that the ground state of C 2
is diamagnetic.
The problem here is that in constructing
5. 12 mixing was allowed only
between orbitals on atoms A and 8 that were identical in energy. Actually,
mixing will take place between all orbitals of proper symmetry, inhibited only
by the fact that if the energy mismatch between orbitals is
mixing will be
reduced . We are therefore justified in dismissing mixing between the I s and 2s
orbitals. The energy difference between the 2s and 2p orbitals is less and varies
with the effective nuclear charge. With a larger z, as in fluorine, the energy
difference is greater and mixing may again be neglected . The difference in
energy between the 2s and 2p levels dramatically increases from about 200 kJ
mol- t in the lithium atom to about2SOO kJ mol- t in fluorine. In the case of the
elements to the left of the series. the lower effective nuclear charge allows the
2s and 2p orbitals to come sufficiently close to mix. This phenomenon is the
equivalent of hybridization in the valence bond theory.
Another way to view this phenomenon is to ignore s-p mixing in the initial
construction of molecular orbitals butthen recognize that molecular orbitals c{
the same symmetry will interact if they are dose enoustt in energy. Thus the
u ..(2s) and u_.(2p) molecular orbitals in a molecule such as 8 2 will interact. As a
result, the lower-energy orbital [u..(2s)) will be stabilized while the higherenergy one [uR(2p)) will become less stable. This leads to a reversal in the
Molecular Ort.ital Theory
t.s
+1- --
--HI
165
ts
la
Fig. 5.13 Correct molecular orbital eneray levels for early elemerus of the first Jona row.
Some mi.Ung (hybridization) has occurred between the 2s and 2p orbirals. N01e that it is
somewhat more diflicuh "to keep books" and determine the bond order here than in
Fia. S. 12: 3u. and I .rb are clearly boodirc (they lie below the atomic orbituls contributina to
them); 4u. and So-,. are essentially nonbondina since they lie between the utomic orbitals
contribwina to them and rouahly symmearicaDy spaced about the''center of aravity ." The
maximum net bond order is therefore one u bond plus two 'IT bonds. The eleCtronic
molecule. Note the unpaired pi electrons.
conliauration shown is for the
energy ordering of the 'lfu(2p) and uR(2p) molecular orbitals (Fig. S. 131 compared to the case for molecules such as F 2 , where essentially no mixing occurs.
lbere will also be some interaction between the
and the o-!(2p) orbilllls.
with the lower-energy orbital becoming stabilized and the higher-energy orbital
being destabilized. However. because these orbitals do not awroach each
other closely in energy. the interaction will be negligible. Note in Fig. 5. 13 that
it is no longer approprinte to use labels such as 2s and 2p to identify the origins
of molecular orbitals. so we merely label them according to their symmetry and
number them in order from the most to the least stable. Thus u.1.2s) becomes
3u",
becomes Su,.. etc.
The magnetic properties of 8 2 and C2 provide strong experimental verification that their electron configurations are based on Ftg. 5.13 rather than on Fig.
5.12. For N 2 (fourteen electrons), either diagram would predict a triple bond
(one u and two .,.) and diamagnetism. consistent with physical measurements.
Experimental evidence supporting one configuration over the other for N 1 has
been sought in photoelectron spectroscopy. The method involves ionizing
electrons in a molecule or atom by subjecting them to radiation of appropriate
energy. When ionizing photons in the ultraviolet range are used, valence-level
electrons are ejected, whereas X rays can be used to ionize inner, core
electrons. The energy of the impingina photons is known from their frequency
(E =
and the kinetic energy () of the ejected electrons can be measured.
166
5 Bonding Modeb in Inorganic Oemistry: 2. The CoWIIenl Bond
The difference between these two quantities (IE) is the amount of energy that
must be provided to overcome the auroction of the nuclei for the ionized
electron:
(5.4 1)
The technique thus can provide valuable infom1ation regarding energies of

occupied molecule orbitals in a molecule since, by Koopmans' theorem, IE
- , where , is the energy or an atomic or molecular orbital. The theorem
assumes that orbital energies are the same in the ion ( Ni in this easel produced
in the photoelectron experiment as in the original molecule. The photoelectron
spectrum of N1 shows that the IE values for the Su.- and I "'u electrons are
about 15.6 and t6.7 eV, respectively, giving - 15.6 and - 16.7 eV as the orbital
energies :md
that sufficient s-p mixing (or molecular oroital interaction) occurs in this molecule to make the Su_. le.vel higher in energy t.han the
I ..... 6 However. ab initio calculations reveal that these two levels are quite
close in energy and may undergo a reversal in their respective orders during
the photoionizat.ion process.J7 In other words, the Koopmans approximation
cannot be assumed to hold for N 1 .
Some molecular orbital results for first- and second-row diatomic molecules, as
well as rdevant experimental data, are summarized in Table S.S.
Bond Lengths an d
Ionization Ene'9ies
Tallie 55
Molecular orbital
for
el.cted cliotamic molecules
.....,h
Further support for the MO descriptions presented in the preceding section comes
from investigation of the bond lengths in some diatomic mol_ecules and ions. For
example. consider the oxygen molecule. As we have seen previously. it has a double
bond resulting from two ubonding electrons. four ,..bonding electrons. and two
Molecvlar ...t.ital pnclictioM

U..paind
Molecule a.m- Net ....... electtolll
(lcJ mol- )
H.
432.00
74.2
lOS
267.2
293
602
941.69
49J.S9
158.9
134
109.8
120.7
141.8
Be2
81
C1
N1
Oz
F1
Nez
2
4
6
8
10
12
14
16
18
20
0
I
0
I
2
3
2
I
0
0
0
0
0
2
0
0
2
0
0
Bond
-.w
bperim-..1 dolo
Dio- or
llond . . .
(pm)
D
D
discussico! or bond enerJies ill Appendia E.
,., Gatdncr. J. L.; Samson. J. A. R. J. CNm. Phys.
ms. 61, 1447-1452.
"Etmler, W. C.: Mclean, A. D. J. CMnt. Ploys. 1910. 7J. 2297- 2303. OeKoc:t. R. L ; Gny. H. 8 .
Cllrmkal
<JJUI BonJinR; Bcn.)ornin/Cwnminp: Menlo Pul<, CA. 1960: pp 212-217 and
238-242.
Moleculor Orbital Theory
167
'IT-anti bonding electrons. The bond length is 121 pm. Addition of two electrons to the
oxygen molecule results in the well-known peroxide
(5.42)
According to Fig. 5.12 these two electrons will enler the ,.. orbitals. decreasing the
bond order to one. Since the compressive forces (bond energy) are reduced and the
repulsive forces (nonbonding electron repulsions) remain the same, the bond length is
increased to 149 pm. If only onr electron is added to an oxygen molecule, the
superoxide ion. o;, results. Because there is one less antibonding electron than in
the bond
is H and the bond length is 126 pm.
Furthermore, ionization of 0 1 to a cation:
oi-.
02--
o; + e-
(5.43)
causes a Jecrtasr in bond length to 112 prn. The electron ionized is a ,.. antibonding
electron and the bond order in
is 21.
The nitric oxide molecule, NO, has a bond length of 115 pm and a bond order of
2!. Ionization to the nitrosyl ion. NO .. , removes an ant.ibonding ,.. electron and
results in a bond order of three (isoelectronic with N 2 ) and a shortening of the bond
length to 106 prn. In contrast. addition of an electron (to a ,.. orbital) causes a
decrease in bond order and an increase in bond length.
The fact that the formation of the nitrosyl ion results from the removal of an
antibonding electron makes the ionization energy (IE) for the reaction
Oi
IE
894 k.l mot-
(5.44)
lower than it is for the unbound atoms of nitrogen (IE

1402 k.l mol- 11 and oxygen
(IE
1314 kJ mol- 1). The nitrosyl ion is thus stabilized and exists in several
compounds. such as NO... HS04 and NO.. BF;.
A comparison of the ionization energies of molecular oxygen and nitrogen illustrates the same point. The ionization energy of molecular nitrogen is 1503 kJ mol- 1,
greater than that of atomic nitrogen, in agreement with Fig. 5. 13 that a bonding (and
therefore more stable) electron is removed. In contrast. the ionization energy of
molecular oxygen is 1164 kJ mot- , less than that of atomic oxygen. In this case the
ionized electron is removed from an antibon<ling orbital. requiring less energy.
Electron Density in
Molecules li2
through F2
The approximate shapes of molecular orbitals have been given previously (fig. 5.1 1).
These give a general idea of the electron distribution in diatomic molecules. Wahl'"
has computed electron density contours for the molecular orbitals of diatomic molecules for H2 to Ne2 . Some examples are shown in Figs. 5. 14 and S. IS. Note particularly that: (I) bonding orbitals cause an increase in electron density between the
nuclei; (2) antibonding orbitals have nodes and reduced electron density between
nuclei; and (3) inner shells (Is in Li. ror example) are so contracted from the higher
effective nuclear charge that they are nearly spherical with almost no overlap and thus
contribute lillie to the overall bonding. We are thus justified in ignoring these core
electrons in detennining the molecular electron configuration (page 163).
Molecular Orbitals
in Heteronuclaar
Diatomic Molecules
In developing a molecular orbital description for heteronuclear diatomics, we need to

take into account the fact that different types of atoms have different capacities to
attract electrons. The ionization potential of fluorine is considerably greater than that
.. Wahl. A C.
1966, lSI. 961.
168
5 Bonding Models in Inorganic Chemistry: 2. The Covalent Bond
(b)
(I)
(d)
(C)
(c)
Fig. 5.14 Electron density contours for (a) H2 ; (b) Li, a,. core; (c) Li2
at
core; (d) Li1 a;z.,;

(e) Li2 tOial electron density. [From Wahl. A. C. Sdnu 1!166. lSI. 961 . Reproduced with
permission.!
of lithium. Likewise. the electron affinity of fluorine is Strongly exothermic but that of
lithium is much less so. and some metals have endothermic electron affinities. A bond
between lithium and fluorine is predominantly ionic, consisting (to a first approximation) of transfer of an electron from the lithium atom to the fluorine atom. Hydrogen is
intermediate in these prOperties between lithium and ftuorine. When it bonds with
lithium the hydrogen atom accepts electron density. but when it bonds with fluorine it ;
loses electron density. All of these bonds, LiH. HF, and LiF, are more or less polar in i
nature in contrast to the bonds discussed previously (page 167). Charge density
169
Fig. 5.15 Electron density COI'llours for various orbitals in lhe 0 1 molecule. (a) Ut.; (b) <Jt;
(C) u,_.; (d)
(e)
(0 total electron density.
Refl"odUCed wilh permission. I
[From Wahl, A. C. Scirnu 1966, lSI, 961.
distributions for these molecules are shown in Fig. 5. 16, which may be compared with
the nonpolar, homonuclear bonus in Figs. S. l4 and S. IS. Cross-sectional density
profiles of several homonuclear and heteronuclear molecules are shown in Fig. S.t7.
Although LiF gives an appearance of being (again, to a first approximation) an ion
pair, in HF the hydrogen atom is deeply embedded in the electron cloud of the fluoride
ion as predicted by Fllians' rules (Chapter 4).
170
5 Bonding Models in lno1ganic O,..,islry: 2. The Covalenl Bone!
IJF
HF
WI
Fig. 5.16 Electron densiay cornours for Lif. HF. and LiH molecules. All molecules drown
co the same scale. The innet" oontours <:$ Fin HF and Li in LiH hove been omitted for
clari1y. !From Bader R. F. W.: Ke.3veny. 1.: C>dc, P. E. I. Chm. Ph.v s. 1967. 47,
3381-3402: Bader. R. F. W.: Bandrouk. A. D. I . Chrm. Phys. 1968.49. 1653-1655.
Reproduced with pennission.J
100.0
-:
10.0
-1M
g
t.O
FF
UHF
J..iF
Fig. 5.17 Toea! electron

<lensiay profiles of simple
molecules along che
iruernuclear axis. [From
Ransil, B. J .; Sinai. J. J.
I . Cl!nn. Phys. 1967. 46,
4050. Reproduced with
permission.!
Molec11tor Ort.itol Theory
171
l1Je treatment of heteronuclear bonds revolves around the concept of

tronegativily. This is simultaneously one of the most imponant and one of the most
difficult problems in chemistry. In the previous discussion of molecular orbitals it was
assumed that the atomic orbitals of the bonding atoms were at the srune energy . In
general, this will be true only for homonuclear bonds. Heteronuclear bonds will be
formed between atoms with orbitals at different energies. When this occurs, the
bonding electrons wiU be more stable in the presence of the nucleus of the atom having
the greater attraction (greater elcctronegativity), thai is, the atom having the lower
atomic energy levels. They will thus spend more time nearer that nucleus. The
electron cloud will be distoned toward that nucleus (see Fig. .5. 16) and the bonding
MO will resemble that AO more than the AO o n the less electronegative atom.
Consider the carbon monoxide molecule, CO. isoelectronic with the N2 molecule.
OXygen is more electronegative than carbon, so the bonding electrons are more stable
if they can spend a larger proportion or their time in the region of the oxygen nucleus.
The electron density on the oxygen atom is greater than that on the carbon atom in
contrast to the symmetrical distribution in the N 2 molecule (Fig. .5. 18). For homonuclear diatomic molecules we have seen that the molecular orbitals are
=
r{t,
o/IA + 1/ts
=.A- h
(5.45)
(5.46)
Both orbitals contribute equally. Now if one atomic: orbital is lower in energy I han the
other. it will contribute mure to the bonding orbilal:
(5.47)
where b > u if atom 8 is more electronegative tluln atom A. Conversely, the more
stable orbital contributes less to the antibonding orbital:
(5.48)
('O
w
Fig. 5.18 (a) Total elearoo density coo1ours for the c:ubon 11101l0Xide tne*Cule. The c:ubon atom is on she lei\. (b) Tow
electron density COOIOUF$ ror the clinitrogen moJecule. [Ftofll Bader. R. F. W.; Bandrauk. A. D. J.
Phys. 1961.49.
16$3. Reproduced wid1 permission.!
172
5 Bonding Models in Inorganic Ch.fllilryo 2. The Co\'alenl lond
In carbon monoxide the bonding molecular orbitals will resemble the atomic o rbiJals
of oxygen more than they resemble those of carbon. The antibonding orbitals resemble the least electronegative element more, in this ca$e the carbon (see Fig. 5.19). This
results from what might be termed the conservation of orbitals. The number c:l
molecular orbitals obtained is equal to the toea! number of a tomic orbitals combined,
and each orbital must be used to the same extent. Thus, if the carbon atomic orbital
contributes less to the bonding molecular orbital, it must contribute more to the
antibonding molecular orbital. The energy level diagram for CO is shown in rl&. 5.20.
(I)
(b)
Fig. 5.19 Diagrommatic sketches o( the molecular ol1>iaaJS in carbon monoxide: (a) ooe
.,. bondill8 ol1>ilal. (b) one ,..
orbilat
Fig. 5.20 En.Jxy level

fOr the molecular OlbiUJs o( carbon monoxide. Noce that
upon bond fonnaaion electrons occupy Mila! thai are more oxygen-like 1han carboo-lila:.
NOte carefuDy the bond order. The Jcrand 3<7 MOs are euenlially nonbondina. The bond
onlet", as in the N1 molecule is lhrft.
Molec:ulor Orbi1al Theory
173
A second feature of heteronuclear molecular orbitals which has been mentioned

previously is the diminished covalent energy of bonds formed from atomic orbitals
of different energies. This may be shown qualitatively by comparing Fig. 5.21 with
Fig. 5.22. This can be seen even more readily in Fig. 5.23. in which the electronegativity difference between atoms A and B is so great as to preclude covalent
bonding. In this case the bonding MO does not differ significantly from the atomic
orbital of B, and so transfer of the two bonding electrons to the bonding MO is
indistinguishable from the simple picture of an ionic bond; the electron on A has been
transferred completely to B.
This extreme situation in which the energy level ofB is so much tower than that of
A that the latter cannot contribute to the bonding may be visualized as follows : If the
energy of atomic orbital B is very much lower than A, the electron will spend essentially all of its time in the vicinity of nucleus B. Although this may be a very stable
situation, it hardly qualifies as a covalent bond or sharing of electrons. In this case,the
sharing of electrons has been drastically reduced, and the covalent energy is negligible. All chemical bonds lie somewhere on the spectrum defined by Figs. 5.21-5.23.
There has been some confusion in the literature concerning the strength of bonds
in situations such as shown in Figs. 5.22 and 5.23. Because good energy match is
necessary for a large A< and good covalent bonding. some workers have concluded,
that f"li!S. 5.22 and 5.23 repre.sent increasingly weak bonding. This is not true. for the
A----(
\\
A---(
\
)----A
\__,t_ta
;---,a\
'\
I
I
"c,
I
Fig. 5.21 Homonuclear

dia1omic molecule, A,.
The covaleru energy is
maximized.
\
\
\
'
)---8
/
a
Fig. 5.22 Heteronuclear molecule. A&+B-. wi1h relatively small eleCJronegaJivity difference
between A and B. Covalency reduced with respect to A, (rJ8. 5.21), but sliD more im(Xlrtan!
lhan 1he ionic coa1ribution.
A---,.------\,.
\
\
\
\
\
\
\
'
----.-----8
llJ;..-o
Fig. 5.23 Heteronuclear molecule, A+s-. wilh large elecJronegativity difrermce. Covalency
is insignificant; the bond is esseOJially ionic.
174
S Bonding Modeh in lnCJI'ganic O.emisii'J! 2. The Cowolenllond
loss of covalent bonding may be compensated by an

in ionic bonding, I
which, as we have seen previously, can be quite strong. In fact, the total of ionic and
covalent bonding may make a very strong bond in the intennediate situation shown in
Fig. 5.22. (Note that the ionic contribution to the bonding does not appear in these
figures.) In fact, the strengthening of a polar bond over a corresponding purelv
covalent one is an important phenomenon.
A second example of a heteronuclear diatomic molecule is hydrogen chloride. In
this molecule the attraction of the chlorine nucleus for electrons is greater than that of
the hydrogen nucleus. The energies of the 3s and 3p orbitals on the chlorine atom are
less than t hat of the Is orbital on hydrogen as a result of the imperfect shielding of the
much larger nuclear charge of chlorine. The molecular orbitals for the hydrogen
chloride molecule are illustrated in Fig. S.24. There is one cr bond holding Jhe atoms
toget her. The remaining six electrons from chlorine occupy nonbonding orbitals,
which are almost unchanged atomic orbitals of chlorine. These nonbonding molecular
orbitals correspond to the lone pair electrons c;( valence bond theory. They represent
the two p orbitals on the chlorine atom that lie perpendicular to the bond axis . They
are therefore orthogonal to the hydrogen Is orbital (Fig. S.8) and have a net overlap of
zero with it. As such, they cannot mix with the hydrogen orbital to form bonding and
antibonding molecular orbitals. The third nonbonding MO is the second of the
hybridized atomic orbitals resulti ng from some 1-p mixing. If the mixing were complete (S0",4 1 character, which is far from the case in HO), it would be the second di
orbital directed away from the bond. Since little mixing of the s orbital of the chlorine
into the bonding MO occurs, the third lone pair is a largely 1 orbital, a distorted sphere
of electron density with the mijor portion behind the chlorine atom.
Although mixing of s and p orbitals is represented in Fig. S.24 as a separate step
pr-eceding the formation of molecular orbitals. the entire process can be combined into
a single step. For example, the bonding molecular orbital in hydrogen chloride may be
considered to be formed as
(5.49)
where ti>J,, o/JJp of!11 are the atomic orbitals on the chlorine (3s and 3pl and hydrogen
(Is) atoms. Now (t and b can be varied relative to each other in such a way that any
amount of p character can be involved in the molecular orbital. For example. ifo = 0.
II
"---1I
/
I
,---,&J
I
\I
II
\
..... \
1
\
/,:==J,,
\---.,
c.,,.\--- /1
1---'
)---
>
HylwMI AOs
---,,
'---J>
Fig. 5.24 EnctJY level diaanm fol' the hydrcsca cNori<lc moJecule. HCI. Tbe mixing d the
.s and p ortilals has been emphasi&ed.
"Fem:ira. R. Owm. PhYJ. Lnr. Jf61. l, 13).
175
the chlorine atom uses a pure p orbital. but if al = ibz. the p character will be 7S"Io (an
"spl hybrid" in VB terminology).:!O And, of course, the relative weighting of a and b
versus c indicales the relative contributions of chlorine versus hydrogen wave functions to the bonding molecular orbital.
Molecular Orbitals
in Triatomic
Molecules and Ions
The linear molecule BeH2 wiU serve as our first example of a triatomic species. The
molecular orbitals for this molecule are constructed from the I.s orbitals on the
hydrogen atoms (labeled H and H' ) and the 2s and one of the 2p orbitals of beryllium
(the one directed along the H-Be- H bond axis). The remaining two 2p orbitals of
beryllium cannot enter into the bonding because they are perpendicular to the molecular axis and thus have zero net overlap with the hydrogen orbitals.
Because four atomic orbitals enter into the bonding, we anticip-dte the formation
of four molecular orbitals. As always, the bonding molecular orbitals are formed by
linear combination of the atomic orbitals to give maximum overlap. Prior to forming
molecular orbitals, we can combine the orbitals of the two hydrogen atoms into group
orbitals that are consistent with the linear geometry of the molecule and with the
symmetries of the atomic orbitals on beryllium. The group orbitals are formed by
simply taking linear combinations of the Is orbitals on H and H'. There are only two
possibilities. so the group orbitals correspond 10 1/Jti + o/IH and 1/Jti - o/IH The first
one is appropriate for overlap with the beryUium 2s orbital, which is everywhere
positive. The second one will form a bonding MO by overlapping with the 2p orbital of
beryllium. which has one positive and one negative lobe. The antibonding orbitals win
be formed by opposite combinations. which give nodes between the bonded atoms.
The molecular orbitals can be repre.sented as
o/1, - n.P..s + blo/IH +
u, 2utr
(5.50)
+ d(o/IH - 1/Jti.) = uu - lu.,
(5.51)
o/lu
1/1;
= bo/lz. -
1/1: = do/12p -
a(o/IH
c(o/IH -
o/IH')
o;
t/tH')
JuN
(5.52)
= 2uu
(5.53)
The parameters a. b, c. and J are weighting coefficie11ts, which are necessary because
of differences i11 electronegativity between Be and H.
The energie s of the BcH, molecular orbitals are shown in Fig. 5.25 and their
electron density boundary surl"aces arc sketched in Fig. 5.26. Both of the bonding
molecular orbitals are de localized over all three acorns. This is a general result of the
MO treatment of polyatomic molecules. Note that the lowest-energy orbital, the lull,
is not shown in either Fig. 5.25 or 5.26. It would be formed from the Is orbital on
beryllium. which interacts very little with the hydrogen orbitals because of the large
energy difference between them. This molecular orbital is therefore nonbonding and is
essentially i11distinguishable from the beryllium Is atomic orbital.
The nitrite ion, N02. is an example of a nonlinear triaiOmic species with 1r as.well
as u bonds. In the valence bond description of the ion. resonance structures are used
10 allow for the distribution of the 1r electrons over all three atoms. The molecular
lO The percenJ s and p chai'DCier is proportional to the 14Uau of the c:oeflicienl5. In the case of
chlorine. the difference in energy between the lr and Jp orbitals is so sreac as to preclude very IOOCil
mixin& ol sand p dw'acter. bu1 it is always possible; the clo$er tl>e
levels are. the more lil<dy
it is Jo occur.
176
5Boncling Modell in lnorgonic Chemistry: 2. The Covalent Bond
,----,z..
x/-,\Jo.
Be
-==_(--
energy levels in the BeH 2

molecule.
II,,...
\\
II
"\
u----- I
\ I
I
fig. 5.25 MolecuiOr orbital
\ I
\\ I
\ \
,,
H lnd H'
) :::::::::::==:: II
If
''
'
I
'21,
fig. 5.26 Anlibonclina

(top) and bondina (bottom)
molecular orbituls In the

BeH2 molecule.
Molecular Orbi1al The ory
1n
orbilal lrearmem provides an alrernare approach !hat does not require resonance
slruc!Ures because elecrrons are automatically delocalized as the merhod is applied.
We can consider lhe u system in NOi' lo consisl of lwo N-0 single bonds
fonned by overlap of sp2 hybrid orbitals on nirrogen and oxygen.21 Also pari of lhe
u nelwork will be four pairs of eleclrons in nonbonding orbilals that are essentially
oxygen sp2 hybrids. (These are lhe oxygen lone pairs in lhe valence bond descriprion.)
Remaining on lhe nilrogen and oxygen atoms are parallel p orbilals (Fig. 5.27). These
orbilals will imeract 10 form bonding and anlibonding combinalions:
ofib = Po 1
Po,
PN
(5.54)
(1r)
o/1,. =Po, + Po, - PN (11*)
(5.55)
As in lhe cases we have seen before , lhe bonding orbital yields a concenrration of
eleclron densily bel ween lhe atoms and the amibonding orbital has nodes between the
atoms (Fig. 5.28). There is a third combination possible:
(5.56)
ofin = Po, - Poz PN

fig. 5:0 Sigma bonds and
lone pairs in the nitrite ion.
NOi'.
Fig. 5.28 Atomic orbitals

(left) and resulting
molecular ortitals (J'ishc) in
lhe nitrile ion: (a) bonding
and (b) aruibonding.
f.IQQ
v
Y-00
_[:)
06-
u H)'bridization is, of course. completely unnec:cssary when using molecUlar ortitaltheory, but is a
convenience here since we are primarily concerned willo che.,. system. The VB and MO treatmentS
of the a system are not sipifieantly different in lloeir results.
178
S 8oflding Models ito lnorgcmic Ch..;&lry: 2. Th Cowll nl Bond
.,;g. 5.29 Two schematic represenlalions at the
orbital in the nitrite ion.
In this case, regardless of the sign given 10 the nitrosen orbital, there will be an
inevitable mismatch-to whatever extent there is positive overlap with one Po orbital
there will be negative overlap with the ocher-producing a nOnbonding situation
(Fig. 5.29).
The molecular orbital result for NO; is similar to that obcained by the valence
bond picture with resonance. There is a bonding pair o( .,. electrons spread over the
nitrogen and two oxygen atoms. The
pair
electrons is nonbonding in the
MO description and effectively localized o n the two oxygen atoms (the node cuts
through the nitrogen atom), but as in the VB picture. they too are smeared over both
oxygen atoms rather than occupying discrete atomic orbitals.
The molecular orbital description fo r the nitrite ion just presented was developed
without the aid of symmetry considerations and as a starting point, it assumed that
u bonds were formed from spl hybrid orbitals on the nitrCJICn and oxygen atoms. Let
us now see how we could have obbined a similar end result by using a method that
involves a more formal application of symmetry and does not invoke hybridization.
(For a review of symmetry in bonding, see Chapter 3.)
As we have seen pictoriaUy in this chapter, in order for a bond to form, the
overtapping orbitals must meet symmetry requirements determined by the type of
bond (u, .,., etc.) and the spatial positions the bonded atoms. This means that the
molecular orbitals for NO; and the atomic orbitals from which they are constructed
must conform 10 the
symmetry of the ion. Consider first the sigma MOs. which
will form a basis for a representation within the C2 point group. By determining this
representation and its irreducible components. we will establish the symmetry criteria
that the contributing atomic orbitals on nitrogen and oxygen
meet, and then can
identify those orbitals. The sigma MOs can be represented as vectors along the N-0
bond axes:
or.,.
or
N
.......
Carrying out the C2,. symmetry operations on these two vectors and recording the
number that are invariant for each operation generates the reducible representation.
r r
r,
= 2
u....,
CTY<
Reduction off,(Eq. 3. 1) yields an o1 and ab 1 as the im:ducible components. In order

for atomic orbitals on nitrogen and oxygen 10 be suitable for linear combination into
Moleculor Obital Theory
179
sigma MOs. they must belong 10 one o f these representations. Our next task is to
choose these qrbitols.
The atomic orbitals on nitrogen contribuling to the bonding will be the outer shell
Js and 2p. By again referring 10 the C 2 character table, we sec that the s and p,
orbitals belong to the a 1 representation while the p, and p1 belong to b1 and b2 ,
respectively. Thus the nitrogen orbitals qualifying for participation in sigma MOs are
the Pv and the s and p . Note that these also are the three orbitals we would have
chosen for
of spl hybrid orbi tals.
By a similar analysis. the nitrogen orbitals capable of participating in ,.bonds can
be identified:
oJ
0
r,
E
2
The C2
Iable sbows that none of the nitrogen valence orbit:1ls transforms as
However. Px transfonns as b1 and therefore can participate in ,. bonding.
Having detennined which nitro111=n orbitals can participate in u and ,. MOs. we
must now identify the o xygen orbitals with Which t hey can combine. More precisely,
we must derive the combinations of oxygen orbitals, or the oxygen group orbitals, that
will meet the symmetry criteria for MO formlllion.n As shown in the treatment of
BeH2 (page 175). group orbitals can be derived by taking linear combinations (additive
and subtractive) of atomic orbitals. The orbit31s of interest here are the outer shell (2s
and 2p) orbitnls of oxygen. The 2s orbitals on the two atoms can be added (s + s) or
subtracted (s - s) 10 give two group orbitals (Fig. 5.30). By applying the C2 symmetrY operations 10 these group orbit.a ls, we lind that the (.r + .r) combination is symmetric with respect to all operotions. and thus belongs to a 1 while the (s - s) combination belongs to b 2 Continuing in a similar fashion with the p orbitals, we see Jhatthe
(p= + P: l
transfonns as a 1 while its subtractive counterpart IP: - P:l
belongs to b2. For (p1 +
and (p1 - p,J we obtain b2 anlltt 1, respectively. Finally.
IPx + Pxl transforms as h 1 and IP.r - P.l as a 2
We now have all the symmetry information needed to construct a molecular
orbital diagr.tm for the nitrite ion. Of course. our symmetry analysis p rovides no
indic.ation o r the relative energies of the o rbitals involved . To obtain such information
would require detailed calculations or experimentation .ll We can. however. make
some reasonable assumptions thai will a Uow us 10 construct a qualitative diagrom.
Because oxygen is more electronegative than nitrogen, the 2s and 2p orbitals on
oxygen will lie lower in energy than the same orbitals on nitrogen. It is on this basis
that the atomic and group orbitals are arranged on the left and right sides or Fig. S.ll.
The nitrogen and oxygen o rbitals that can combine to form sigma MOs are all of those
., Whereas the
piacrial aj)p'OQdl uoc4 here ror clerivlrc the ox)llen poo.op orbilals ond dctctmimna
their symmetric$ is suitoble ror N02. more tOmpinlcd molecules Uld ions
lhosc
invclvina cle&CII!Cr.IOesl aencniJy require more aophisricalcd methods. For
ol lhese
mclhods, the Wefeslcd reaclu should rcftr 10 the aroup theorY lUIS in FOOIIIOIC I ol Chaprer ) .
"' Harris, L E. J. Clwm. Ploys. 1973, 58, S6Js-S616.
180
5 loJiding Models in Inorganic Chetnislty: 2. The Covalent lond
<; a., "r-
t a,
II+ II
(J- 1)
-1
(o)
1 1>,
101
-1 -1
-1
-1
I 1>,
(b)
(C)
-t
-1
"2
(d)
Fig. 5.30 The atomic orbitals of the nitrite ion when viewed o.lor1s 1he z axis. which i$ Jhe
principal twofold axis or the anoin. (a) the p1 and p1 atomic orbitals on nitroseo: The plane c:l
the anion is 1he yz plane, and the x axis is perpendicular to thai plane. (b) The aJomic p
orbiUIIs of the ldl-hand oxygen atom. Note thQJ the z axis has been redefined alons 1he
O-N bond axis.
axis is still perpendicular to the plane or the molecule, and Jhe y axis
must be mu1ually perpendicular 10 x and z, (c) The atomlc p orbitals of the risht-hand oxygen
atom. Apin, the z axis has been redefined alons the N- O bond uxis, and x andy are
mu1ually perpendicular. (d) Group orbilats for he oxysen aJOms in NOj. derived from 1he 2s
and 2p atomic orbit:lls. The orienwions are as shown in parts !b) and (c).
symmetries. Taking the a 1 category first, we lind a total of live

that have a 1
orbitals (two from nitrogen a.nd three oxygen group orbitals). which will result in five
molecular orbitals. In estimating the relative energies of these molecular orbitals. we
should bear in mind that two factors will promote stabilization of a bonding molecular
orbital formed from two intel'llCting orbitals: favorable overlap and similarity in
energy. The degree to which these two factors are present or absent wiD determine
whether a molecular orbital is bonding (with an anti
counterpart) or essentialy
nonbonding. Thus we would predict (on the biUis of a rather latge energy gap) that the
(.s + s) oxyge.n group orbital and the nitrogen a 1 orbitals will lead to an a 1 molerular
orbital that is only slightly bonding. Overlap and energy match are more favorable for
181
, - - - b ! ( I - S)
u:___jL, ...
Fig. 5.31 Molecular orbital
, ,',
..,,'
, - - - o 1 fs+.l)
ror the nitrile ion.
the (p, + P;) group orbital and the

a, orbitals, so they would be expected to
combine to form a strongly bondin&: and strongly antibondin&: pair of MOs. On the
basis of poor overlap between t he (pY - Py) llfOup orbital and the a 1 orbitals on
nitrogen, we can assign this group orbital as an essentially nonbondin&:"o MO.
By applying similar reasoning to the b1 orbitals (four in all), we conclude that the
nitrogen orbital of this symmetry will overlap to yield a slightl y bonding MO with the
(s - s) group orbital and a distinctly bonding MO with the IP: - P:> group orbital.
The (pY + p,) group orbital will be essentially nonbondin&: and there wib be one
antibonding MO. Finally, the nitrogen b 1 orbital will combine with the
+ group
orbital to form bonding and antibondin&: .,. MOs.
Of the twelve molecular orbitals constructed, the nine that are lowest in energy
will be occupied by the valence electrons in NOi . The electrons in the lowest level a,
and b2 orbitals are only slightly bonding and may be thought of as lone pairs on the
oxygen aJoms. The Lewis st.ructure for NO; includes three additional lone pairs on
the two oxygen atoms. ln the MO picture, they are the electrons in the a 1 IPy - Py)
and b2 (Py + p,) orbitals-which we have already identified as essentially
ing-and those in the a 2 orbital, which is strictly nonbonding because the
group
orbital has no symmetry match on nitrogen. The nonbonding electron pair that is
shown in the Lewis structure as residing on nitrogen corresponds to the pair in the
highest occupied molecular ortital (the HOMO) in the MO diagram. The final result.
then. for our molecular orbital description is two u bonds, one .,. bond, and six
az
182
5 S.nd ing Models in Inorganic Chemistry: 2. Th Covolenl lond
nonbonding electron pairs. It should be emphasized that the diagram in r.g. 5.31 is
oversimplified because it shows only the major interoct ions between orbitals. There
wiD actually be some interaction between aU orbilllls or the same symmetry. In other
words, the diagram suggests more localization of electrons than is actually the case.
The orbitals shown in Figs. 5.28 and 5.29 correspond to the b 1 ,.. molecular orbitals
(bonding and antibonding) and the a 2 nonbonding orbital in the MO diagram.
Electronegativity
Linus Pauling first defined electronegativity and suggested methods for its estimation.
Pauling's definition2 has not been improved upon: The power of on atom in o
molec11le to attract electrons to itself. It is evident from this definition that elec
tronegativity is not a property of the isolated atom (bit hough it may be related 10 such
propenies) but rather a property of an atom in a molecule , in the environment and
under the influence of surrounding atoms. One must also note that the "power to
attract'' is merely another way of describU. the "reluctance to release" electrons
from itself to a more electronegative element.
Pauling based his scale on thermochemical data. We shall examine his methods
shortly, but we may note that his scale is an arbilr.lrY one chosen so that hydrogen is
given a value of about 2 and the most electronegative element, fluorine, has a value of
about4:
H - 2.2
Li
Na
= 2.S
1.0
0.9 Mg = 1.3 AI 1.6 Si "' 1.9
Be = 1.6
8 2.0 C
N 3.0 0 = 3.4
P 2.2
= 4.0
S = 2.6 0 3.2
There are other scales that have absolute units. and whereas it might seem at fim
glance that an absolute scale would be preferable, the Pauling scule has a familiarity
and anendant literature that no absolute st:lle can come close to matching. Familiarity
as a virtue should not be discounted in unthinking anempts to "standardize t hings.
Several times workers have reported erroneous elect ronegativity values in electron
volts or in MJ mot- that they would have instantlllleously noticed und rejected if they
had convened their val ues to the Pauling scale. A value of 3.3 for fluorine st.'lnds out
like the proverbial sore
Consider Pauling's approach to the treatment of a molecule or hyc.lrogcn chloride
which is usually represented today as
H&+CI 6 Thc usc of li 10 represent partial charges in a polar molecule is rdativcly recent.
Pauling would have pictured it as
(5.57)
It
2A
Ill
L Tlw Ntuurt o/IM dwnrkol Bottd,lrd ed.: Cornel Univcnity: llb;Ja, NY, 1960: p 88.
l..iobmoa. I. P.; Hubeey,l. E. Phy.s. R,v. D 1911. J6, ISS9-IS61.
EleclrCiaegatlv;ty
183
where the wave 1\Jnotion of the rcsonanc:e hybrid would be

(5.58)
1/1= X!/lcov + Yt/1+ - + i.l/1-+
where x. y, and t are weighting coefficients and cov. + - , and - + are labels for
contributing canonical forms I. II, and Ill . If chlorine is more electronegative than
hydrogen, contributing form II will be impa1ant as well as form I ( HO is predominantly covalent), but form Ill, which places a positive charge on the chlorine atom,
makes a negligible contribution. Pauling assumed that resonance would stabilize the
molecule
HO and that the greater the contribution of II, the more polar the
molecule and the greater its stability. Soon arter Pauling published his first paper on
electronegativity, MullikenZ6 suggested a method for estimating how much each of the
forms I, 11. and Ill would contribute to the hybrid and used it to esu1blish the
electronegativity scale that bears his name.
or
Mulliken- JoHe
Electronegativities
The met hod of treating electronegativitics that has the firmest theoretical basis is the
Mulliken-Jalft system. Recall that canonical forms that are low in energy and stable
contribute the most to the resonance hybrid, and that high-energy forms contribute
little. Mulliken suggested that two energies associated With an atom should reflect a
measure of its electronegativity: ( I) the ioniz,ation energy, as a measure of the
difficulty of removing ao electron (or, more generally, electron density) to form a
positive species; (2) the electron offinily, as a measure of the tendency of an atom to
form a negative species. Structure II is slllble because chlorine has a hiah electron
affinity and hydrogen has a relatively low ionization energy for a nonmetal. Structure
Ill is unstable because chlorine has a high ionization ene rgy and hydf01:Cn has a low
eleclron affinity. Mulliken's definition of electronegativity is given simply us
IE.+ EA.
(5.59)
or. when the energies are in electron volts (the most common unit used in the past).
putting the values on the Pauling scale:
XM - 0.336[
IE, + EA.
2
- 0.615
(5.60)
or. when the energies arc in MJ

XM = 3.48 [
IE, + EA.
l
- 0.0602
(5.6 1)
Now it should be recalled that the first ionization energy and the electron affinity
are merely two of the multiple ionization potential-electron affinity energies that fit a
polynomial equation (see Chapter 2) that is quire close to being quadratic (I he coefficient.s of the higher order terms arc small). Jafft and coworkersz have pointed out
,. Mulliken. R. S. J.
Phys. 1934. l. 782-793; 19JS, J. S1J-S8S.
11 Tbls simple,linear n:la1ionship ialhe mosa (requenlly used. However. Bratsch !see Footnoac 28lllld
Table 5.6) t.s pn:sellled evidence ror a samc:whaa beaaerfil&inl quadraajc rcllnionship.
:&1
Hinze. J .:
H. H. J. Am. C'lkom. So<:. 1"2, 34, 540-S46; J. Phys. Cltvn. 1963.67, tSOI-IS06;
Hinu, J.: Whiachead. M. A.: Jalff. H. H. J. Am.
So<:. 1963,85. 14&-154. Sec also Bnuch,
S. G. J. CMm. Jut:. '"' 6$. l441. 223-227.
184
5 Bonding Models in Inorganic Chemist.y: 2. The Covalent land
that if the energy curve (see Fig. S.32) is used in this form. the Mulliken definition of
electronegativity is equal to the slope of the curve as it passes through the origin:
E =aq+(Jql
X= dE/dq
(5.62)
= a+ 2{3q
(5.63)
This formulation provides clear intuitive perspective: II indicates that an atom will be
highly electronegative if it releases much energy (because its energy curve is steep) as
it acquires electron density; an01her atom will be less electronegative because its
curve i.s less steep and, when combined with tht mort electronegative atom. il does
not cost as much energy climbing its own tnergy curve. A molecule ofCIF will exist as
Qe+pa-. and it will be more stable than a hypothetical nonpolar OF molecule.
The relationship between the Mulliken definition and that of
can be shown
quite simply. Taking Eq. 5 .62and substituting q = + I, we know that the energy, E,of
the system wiU be that of the + I cation, or the first ionization ene.rgy. Likewise for
q
-I . the energy will be the negativel!l of the electron affinity, so:
IE,. = E+ 1 = a(+ I) + Jl( + 1)1
(5.64)
and
-EAY
= E_ ,
I)+ 13( - 1)1
(5.65)
Subtracting Eq. S.65 from Eq. S.64 gives:
IE,. + EAv
(5.66)
2a
which yields a as the Mulliken elecuonegativity (Eq. S.S9).

+J
-1
Fig. 5.32 Ionization

aJ'IiNty
curves fot fluorine and
chlorine. The e lectrOnea:uivities are sivcn by the
slopes ot these curves. Ttlis
flaure is an enlaraed portion
ot Fia. 2. 13.
-0.8
-{).6
-0.4
-O.l
+0..2
a....
29 Note that lhc defitlili<ln or electron .mo;.y doe$ no1
f'olow the u.ual thennodynamie c:onvention in

d!at a posiJivr decuon .Binity is atXhnmk. See Chapter 2.
Electronegativity
185
A word must be said here concerning the subscript v's in the above equations.
They refer to Jhe valence state. Just as Pauling's definition of electronegativity is for
an atom in a molecule , the Mulliken-Jaffl! detinilion of electronegativity for various
hybridizations involves the computation of valence state
ent!rgies and
valence state electron affinities by adjusting for the promotion energy from the ground
state. The valence state ionization energy and electron affinity are not the experimenas it exists
tally observed values but those calculated for the atom in its valence
in a molecule. Two short examples will clarify the nature or these quantities .
Divalent beryUium bonds through two equivalent sp. or digonal, hybrids. The
appropriate ionization energy therefore is not that of ground slate beryUium. lsl2s2,
but an average of those energies necessary to remove electrons from the promoted,
valence stale:
lsl2s'2pl ____. Jsl2sl2p0 (JEP) and
lsl2sl2pl -
ls12.f02pl (IE,)
(5.67)
II is thus possible to calculale the hypothetical energy necessary to remove an electron

from an sp hybrid orbital. This VSIE (and the CQcTesponding valence state electron
affinity) can be used to calculate the e.lectronegativity of an sp (dt) orbital.
A chlorine alom may well be assumed to use a pure p orbital with hybridization
neglected. but still the valence state ionization energy does not correspond to the
experimentally observed quantity. We may consider thai the use of ionization energies
and electron affinities relates to the occurrence or covalent-ionic reso1\311U as shown
previously in Eq. S.S1. Now one of the requisites for resonance 10 occur is that all
contributing forms have the same number of unpaired electrons (page 14S), so the
wave function and energy for any contributions from c1 must be for zero spin (all
simple molecules containing chlorine are diamagnetic). The ground state ionization
energy corresponds to the process
_,. Cl.(lP), but the VSIE is for ionization to
a singlet state for a, a suitably weighted a verage of tS and 'D. We need not concern
ourselves with the mechanicslO of calculat ing the necessary promotion energies for
either beryllium or chlorine. but we should remember that it is not possible to
calculate accurate electronegaJivities simply from ground state ionization energies and
electron affinities alone .
One oft he strengths of the Mulliken-Jufl'l! approach is that it is capable of treating
the electronegativity of partially charged atoms. We shoukl not expect an atom that
has lost electron density to have the same electronegutivity as a similu atom that has
not had such a loss: the former should be expected to hold on to its remaining electron
density more tightly. Conversely, as un lllOm acquires a partial negative charge, its
This can be shown readily by
attraction for more electron density will
r ewriting Eq. S.63 as
X = dE/d6 = a
b6
(5.68)
in which the partial charge, 6, replaces the ionic charge, q, and the constants have
been changed for convenience (a = a ; b 2/3).
The importance ofthis equation lies in illustrating the large effect that charge can
have on the electroneptivity of an atom. Intuitively, one would expect an atom with a
positive charge to be more electronegative t han that same atom with a negative
)0
See Mallin. W. Ptoc. Rqy. S. (L<>nc/onl lt50, .11201, 548. For Yety readable 3CCOUO!Js d lhe
Y:llence swe sec Mc:Weetl)', R.
Oxl'onl
London. 1979; pp ISO,
20t-203, 203-209; Jolvlson, D. A. $onw TlttrrrwdynDfflk
<If I--Ronic
2nd eeL;
Carnbridec
CatnbridJc, t 982; pp 176-ln. 200-206.
186
5 landing Modell In Inorganic Che...;stry: 2. The Cowalent lond
charge. Eq. .5.68 allows us to quantify that effect: An iodine atom with a partial charge
of about + 0.4 is almost as elecrronegative as a neutra.l fluorine atom . The si8nificance

of the parameters a and b is clear. The inherent or neHtral atom electronegativity is
given by a . This is the electronegativity of an atom in a particular valence state as
estimated by t.he Mulliken method and corresponds to similar estimates of electronegativity by Pauling (Xp), Allred and Rochow (XAR) and others (see Table .5.6). It
may be used alone (XMJ = a) to say, for example, that in LiH the hydrogen atom (a =
2.25) is much more electronegarive than is lithium (a ,. 0.97), and should be wriuen
Li.r"Ho or even Li'"H-.
The parameter b is the chorge coefficient. It measures the rate of change of
electronegativity with charge. Mathematically. b is the second derivative of energy
(first derivative of elecrronegativity) with respect to charge:
b
= J2/diJ2
= dx/d6 - IE, - EA.
(5.69)
It thus defines the curvature of the energy-charge parabola. O!emically, it is the

inverse of the charge capacity
or polarizability:ll
b = 1/1<
(5.70)
Large, soft, polarizable atoms have low values of b, and small, haJd. nonpolarizable
atoms tend to have higher values. An atom with a large charge coefficiem will change
electronegativity much more rapidly than one with a lower value of b. Thus a srnaiJ
atom (low " large b) has only a limited ability to donate Of absorb electron density
before its electronegativity changes too much fOf further elecaron uansfer to roke
place. One of lhe most imporront examples is the very electronegative but very small
fluorine atom. Although initially very electronegative when neuaral (note the steep
slope at the origin of Fig. .5.32). it rapidly becomes "saturated" as it accepts electron
density (note how quickly the slope llauens out between - 0.4 and - 0.6). and beyond
-o.7. it is necessary "to push" to get more electron density onto a fluorine atom. This
is closely related to the comparatively low electron affinity of fluorine (Chapter 2).
The charge capacity effect is responsible for the well known inductive effect of
alkyl groups (see page 196). It is also important in hard and soft acid-base theory (see
Chapter 9). and causes several other unexpected effe<:ts.l2Jt is basically a polarization
effec.r in which larger atoms and groups can IICquire or donate large amounts of
electron density without unfavorable energy changes.ll
Recent Advances in
Electronegotivity
Theowy
The advances in recent years have been more evolutionary than revolutionary. Increasingly, MuUiken's original idea of expressing elect ronegativity in aerms of the
energy of valence electrons has come in.ro favor, and the other definitions in terms of
resonance energy or algebraic relationships of size and charge have been viewed as
useful approxiii18Jions when orbital eneJ'Iies are not available. In addition. the relationship between electronegativity and acidity and basicity, always intimate, has been
extended further (see Olapter 9).
"PoliiZer. P. J . Clrmr. l'ltys. lti7, 1J6. ton-t07l.

" Polilzer, P.; Huheey, J . E.; Mumy. J. S.; Crodzickl. M. J. Mol. Srmcturt (THEOCHEM), t992.
ZS9, 99-120.
Huhoey. J. E. J . Org. Owm. mt . .J6, 204-lOS. Poliuer. P.; Mumy, J . S,; Gric.es. J: E. In
Chnnical HDrdnns: Sen, K. 0 . Ed.;
Betlin, in p-eas.
Ele<tronegativity
Tahle5.6
Electronegativirin of the ...........,
Rodoow
or
hybrid
Element
2.20
- b
Allred-
2.59
2.30
Volts
scale/
2.25
7.17
12.84
3.4912.98<>
23.22
2. He
4.861
IS.OSB
0.97
3.00
4.77
3. Li
0.89
0.97
0.91
0.98
4. Be
1.57
1.81
1.47
1.58
1.54
4.65 - 6.58
2.05
2.04
6.37 '
8.74
5. B
2.04
2.28
i .OI
5.86
8.64
1.90
2.50
sp
2. 99
10.42
11.70
6. c
2.55
2.75
2.S4
spl
2.66
8.91
II ..SO
sp3
2.48
8. IS
11.39
3.07
3.68
14.00
13.32
7. N
3.04
3.07
3.19
3.26
11.78
13.22
10.66
13.16
3.04
2.90
10.00
13. 13
p
2.28
7.32
13.00
3.61
spl
8. 0
3.65
3.50
3.94
15.48
15.62
3.44
sp3
3.68
14.02
15.55
3.41
12.55
15.47
11"/..s
p
2.82
9.63
15.33
spl
3.98
4.00
4. 19
17.63
17.99
4.30
4. 10
9. F
15.30
17.81
3.91
14%s
p
3.35
12.20
17.57
10. Ne
4.5QII
4.846
4.79
sp3
4.49
18.86
18.92
12"/.s
IS)f
1 8.50
3.98
p
3.41
12.56
18.08
4.261
13.296
0.87
s
0.91
2.84
4.59
II. Na
0 .93
o.w
1.01
1.29
1.23
sp
1.37
4.11
5.21
12. Mg
1.31
1.32
p
0.91
2.86
6.23
13. Al(l)
0.84
Al(lll)
1.71
1.47
1.61
spz
1.83
5.61
6.12
1.61
sp3
1.71
5.21
5.92
2.!4h
1.92
spl
2.28
7.30
7.13
1.74
14. Si
1.90
2.19
2.06
spl
2.41
7.84
9.53
2.25
IS. P
2.52
20/'..s
2.30
. 7.41
9.39
p
1.84
5.67
8.83
16. s
2.58
2.96
2.44
2.59
sp3
2.86
9.84
10.36
11"/.s
2.69
9.04
10.20
p
2.31
7.44
10. 12
2.83
2.87
14"/.s
. 3.10
12.15 , _ 11.55
17. Cl
3.16 - 3.48
.
p
2.76
10.9S
11.40
18. Ar
3.31h
3.2Q.f
3.24
sp3
3.49
12.98
12.38
12%s
3.19
11.41 . 12. 18
-
+' ; _
' - p
2.86"
9.83- i- -11.981
"<.i-rl-.t
_!..
.Jr ': (' .;
i,
9.87,
....,
r.... :1;<
.,. .. ' - 3:11
19. K
0.82 ., 0.45
. 0.91
0.73
s l
0.73 , . 2.42 :!3.84
. 1.00
0.95 ' . 104 . ' 1.03 . -sp-3rr.-1....;;..--...ila..
.
1.08 ..........
: t 3.29 .. ,.,iil.:1!.jj
20. Ca
- - - - - - - __ ...... . 'P.)
I. H
2.20
S.SOt
Pouling
tf':'
...
..
-:
... ,_,. ...,....
..,,
t-1'
l\
188
5 Bonding Models in Inorganic Chemistry: 2. The Covalent Bond
Tal.&e 5.6
"'Allred
. Orbital
or
iod.ow
Pauling or
scale'
Volts -
hybrid
21. Sc(lll)
22. Ti(ll)
Ti(lll)
T'I(IV)
23. V(ll)
V(III)
1.36
1.02
U4
0.73
1.20
I.SO
0.69
1.39
2.51
1.63'
1-32
1.45
1.66
O(rii)
1.66
Cr(VI)
3.37
25. Mn(U)
. 1.56
1.66
l..S.S
1.60
2.20
Mn(lll)
Mn(IV)
Mn(V)
Mn(Vl)
Mn(VI[)
26. Fe(ll)
Fe(lll)
27. Co(([)
Co(lll)
28. Ni(ll)
_ _
Cu{JI)
30. Zn
31. Ga(l)
Ga(lll)
32. Ge(ll)
Ge{JV)
33. As(lll)
2.74
3.28
3.82
4.36?
1.83}
1.64
1.96
2.20
1.88
1.96
2.S6
1.91
1.94
_1,20_ _ 2.03
2.00
1.98 - -1.65
2.23
0.86
1.81
2.42
0.56
2.01
2.62
2.18
2.82
3.01
3S. Br
_'l:
.. .
' ...
2.96
'
&
3.22 .;
>.:.r- ......
._,
electron
1.09
V(V)
24. 0(11)
*'
b
Volts/
.,..:
1.64
1.7
1.75
1.75
s
1.49
4.48
6.SO
- - -- - -- - - - - - - -- - - 1.66
Sp
1.65
4.99
5.91
p
0.81
2.7S
6.36
1.82
1.76
spl
2.01
6.28
6.22
p
1.30
3.92
7.63
2.02
1.99
spl
2.33
7.S3
7.62
2.20
2.21
spl
2.38
7.70
8.98
20"/.s
2.26
7.25
8.8S
p
1.68
5.45
8.34
2.48 , ' 2.42
spl
2.79
9.48
9.70
-:15
- 11"/.l ' 2.60
8.65
9.S9
p
.
2.20
6.99
9.39
2.74
2.68 : ..14"/.s
2.95
10.25 . 10.41
:0
J:
p 0C
-; 2.60
C 8.63 !: 10.22
I
r;i
'l
1
:
)1!.-ii,::;..:I'" J ..,
1,
2.66- .; 8.9J-t i, 10.58
;:;
....
0.71
2.n
0.82
\ s.u. .. 2.33
.I
Electronegativity
Table 5.6
of tNt elements (Comimled)
...... . .g_ ,_
- . -;;-:-'..;-Air.a:..Salidenon
Element
xt
xs
42. Mo(ll)
Mo(IU)
Mo(IV)
Mo(V)
Mo(VI)
43. Tc
44. Ru
45. Rh
46. Pd
47. Ag(f)
2.16
2. 19
0 .90
2.24
2.27
2.35
1.9
2.2
2.28 2.20
1.93
48. Cd(II)
49. ln(l)
ln(m)
50. Sn(U)
Sn{IY)
51. Sb
52. Te
1.15
1.40
1.73
- 2.20 -
- -::- 1.45 1.83
1.35
...
-::
1.42
s
sp
sp
1.46_
1.78
1.80
1.96
2.05
2. 14'
1.49 -:-
.f ""ft'X; '
1.66
.. ...r..i 1.?2::.
2.46/o
1.82 :
,
.;r
2.62
;i' '
2.01 J
1.82
1.98
2.. 16
,2 21.-.L-... 2.36 -
. .
2.34/1 '
-J
<:.
0.79
0.89
1. 10
. ss.
- 6S. Tb
66.Dy
Ho
Er
0.22
0.68 .J
.0.86
-: 0.97
p
spl
11"/.s
p
spl
14"/.s
'2.40. -
T "1.
30"/.s
spl
spl
20"/.s
'
55. Cs
S6. Ba
S7. La
Ce
59. Pr
60. Nd
i 61. Pm
62. Sm
63. Eu .
1
' 64, Gd -
'volts
IJ6
1.98 . ,
2.606
Volih/
electron
1.42
- - - 2.66 - -2.78
54. Xe
Pauling
scale'
IJO -
1.69
2.1
Orbital
or
x.,.c
--:.Xu 4
.. -,
- 53. I
Allen
2.58
P
spl
1-../.s
p
s
sp
1.47
4.44
6.27
1.53
1. 12
1.76
1.85
2.21
2.22
2. 12
1.67
2.57
2.41
2.06
2.95
2.74
2.45
3.01
2.73
2.44<>
2.40r
0.62
0.88
4.62
3.40
5.39
6.09
7.05
7.09
6.68
5 .08
8.52
7.83
6.46
10.26
9.29
8.00
10.52
9.24
7.96a
7.761
2.18
2.79
5.91
6.11
6.63
6.97
5.04
8.16
8.02
7.45
'8.74
8.64
8.44
9.38
9.33
9.2S
9.52
9.36
9.21
3.42
3.93
1.12 .., -
1.13
1.14
.
1.17
.,,
., to '_,.
-i
- __;; ---.=--. -
--
5 Bonding Models in Inorganic a.-iatry: 2. The Covalent Bond
190
Table 5.6
Utctronegativities of the .........., (Cot!tinued)
Mullilc.,._Jalf6, Xw0
Element
73. Ta
74. W(ll)
W(lll)
W(Vl}
75. Re
76. Os
1!0 ,Jjg
81. nm
n(lll)
82. Pb(tl)
I<"Pb(IV)
83. Bi
84. Po
85. At
86. Rn
87. Fr
88. Ra
89. Ac
90: Th
91.- Pa
93. Np
94.Pu
95.Am
96. Cm
97. Ilk
98.a
99.Es
100. Fm
101. Md
102. No ,
Alen
or
"Xu J
x-
hybrid
1.9
2.2
2.20
2.28
2.54
2 .00
1.62
2.04
1.87
2.33
2.02
2.0
2.2
77. Ir
92.
Pou&ng _. Smrdenon
1.5
2.36
78. Pt
79. Au
'
Orloital
Al..dRochow
0 .7
0 .9
1. 1
1.3
1.5 - 1.38
1.36
1.28
1.3
1.3
1.3
1.3
1.3
1.3
1.3
1.3
..
0 .73
0 .98
1.67
Pauling
scale'
Volts
Volts/
.!ectron
5 .71
5.55
2.50
6.08
3.S2
7.82
6.81
8.14
9.76
6.92
5.81
5.92
6.40
7.47
5.32
8.09
8.81
10.03
6.92<
2.30
2.88
3.40
3.69
" /.33
1.40
/.46
1.52
2.20
0.99
2.25
1.92
2.291<
2.34
/.55
/ .44
1.41
1.44
s
sp
p
1.44
1.5
1.67
1.76
1.90
2.066
0.86
0.97
1.00
1.11
1.14
1.22
1.22
1.22
(1.2)
(1.2)
(1.2)
(1.2)
(1.2)
(1.2)
(1.2)
(1.2)
sp2
p
spl
20"/.s
17"/.s
14"/.s
p
p
s
sp
1.87
1.81
0.76
1.96
1.16
2.41
2.15
2.48
2.85
2.55
2.12<
0.68
0.92
'
Electronegativity
191
Two recent approaches should be mentioned. In one. Parr and others).& have
followed Mulliken by defining electronegalivity in terms of ionization energy and
electron affinit y. They have also advanced the idea of electronegativiry in terms of
density functional theory. This is a close parallel to the
system in its
emphasis upon the first and second derivatives of the ionization potential-electron
affinity energy curves. In addition, it provides quantum mechanical support for the
intuitively appealing idea of electronesativity equalization (see Pa&e 198). It differs
only to the extent that those using this method have tended to use ground state values
instead of valence state values.
More recently Allen:U has proposed that electronegativity be defined in terms of
the average one-electron enersy of valence shell elect rons in ground-state free atoms
which may be obtained spectroscopically. This quantity is termed the configuration
energy:
CE =me,+ ne,
m + n
(S.71)
where e, and e,. m and n ace the energies and numbers of electrons in the p and s
orbitals of the valence shell. respectively. The result is another strong argument for
defining electroneptivity (X,pec) in terms of orbital energy. This system of electroneaativity has been successfully applied to periodic properties of the elements such
as covalent. metallic, and ionic bonding; atomic radii: multiple bonding; oxidation
states; and the unique properties of cartlon and hydrogen. Nore, however, that these
energies are not valence state energies, nor does the calculation include electron
aflinities.l6 This prevents application to the effect of charge capacity (hardness and
softness) as related to electronegativity or to the variability of electronegativity with
hybridization (see beloW). On the other hand it presents an unambiguous measure of
an atom"s average electronesativity. Further efforts to apply the method to transition
metals and to changes in oxidation states will probably be forthcoming.
The articles by Allen cited above are also recommended as the most recent review
of various aspects of electronegativity theories and for the idea that electronegativity
is " the third dimension of the periodic chart."
Voriotion of
Electronegotivity
Although clectronegalivity is often treated as tho ugh it were an invnriant property of

an atom. we have seen that it depends on two properties: valence state (hybridization}
and atomic charge. Hybridization affects electronegntivity because of the lower energy and hence greater electron-auracting power of s orbitals. We might expect the
electronegalivity of an atom to vary slightly with hybridization. with those orbitals
having greater s character being more electronegative. Some results of the variation in
,. Pnrr, R. C. Ann.
Chm. t983.
6JI-6.56. Pclitur, P.: Weimtein, H. J. Chm. l'hys.
1979. 7t, 4218-4220. Van Cenechlen. K. A.; Morlicr, W. J. Zlolitn IMS. &. :ln-283. Pearson,
R. C. Ace. Clwm. /l.u. 19ft. 1J, 1-2.
lS
Allen. L C. J. Am. C'llm. S. 1989, II/, 900J-90t4: A. Clvm. R 19ft, 1J, t7S-176; J. Am.
Clwm. Soc. 1991.114, 13 t0-ISI I; Co,. J . Clwm. tm, 70. 63 1-6)S. NOie that Allen'up<ciroscopic
dc<:II'Onepllvity,lilce MIA!ilten's, wil - ' l y be exprcued;, t<tWGddc<:lroft Wills, but can be
convc:rml to the Plwina ac.le iC desirtd.
u It should be nc1e11 thai inasmuc.b &S the ionlulion enern or most -
is an mler of rnqnilucle
the c11r011 alfftly. d<cttonc:plivily methods which are 1\lndam<ftt..y rebled Otl1y to
iclnizalion en<flPes are sliiJU<CcssN.
192
5 Bonding Modela in Inorganic Chemistry: 2. 'The Covalent Bond
electronegativity have been given by Bent.l7 One factor affecting the acidity of
hydrogen is the difference in electronegativity between the hydrogen atom and the
atom to which it is bonded.J8 Methane, CH4 , with spJ hybridization and 2.5"/. s
character is rather unreactive. The electronegativity of tetrahedral carbon is nearly the
same as that of hydrogen. In ethylene, the carbon atom is hybridized approximately
spl and the hydrogen atom is somewhat more reactive, reflecting the increased
electronegativity of carbon with 33% s charactef". Finally. acetylene has hydrogen
atoms which are definitely acidic; salts such as Ca2.. C;zC2- form rather easily. In
this case the digonally hybridized carbon atom (SO"/. s character) has about the same
electronegativity as a chlorine atom.
The basicity of amines is a funaion of the hybridization of the nitrogen atom.J9
The more electronegative the nitrogen atom, r:he less readily it will share its lone pair
electrons and act as a base. The series of nitrogen bases, aliphatic amines. pyridine,
and nitrites, exhibits this property:
-2S%s
Me 1 N: + H 20
33% s
C N : + H20
SO%s
MeC.aN:+ H 2 0
Me 1 NH + OH-
pK= 4.2
(S.72)
CNH +OH-
pK6
=8.8
(5.73)
reaction
(5.74)
The electronegativity of the nitrogen atom increases as the s character of the hybridization increases, and hence its basicity decreases .
Another interesting case has been given by Streitwieser and coworkers.40 It has
been found that strained ring systems of the type shown in Fig. 5.33 are much more
reactive at position No. I than at No. 2 in reactions involving loss of positive
hydrogen. The strain in the four-membered ring results in the use of more p character
in these bonds by the Cto atom (the shaded orbitals in Fig. 5.33). The corre.sponding
increased s character in the bond to C 1 causes a greater electronegativity. an induced
positive charge, and a greater acidity of the hydrogen atom. In the related pyridine
derivative with a nitrogen atom in place of C 1, the same phenomenon results in
reduced electron density on the nitrogen atom and reduced basicity compared to ahe
unconstrained analogues.4 '
The electronegativity of an atom can vary in response to the partial charge
induced by substituent atoms or groups. For example. methyl iodide hydrolyzes as
expected for alkyl halides , but trif!uoromethyl iodide gives unusual products:
J1
)II
CH3 1 + OH- --... CH10H + 1-
(5.75)
CF31 + OH- - - CF3 H + 10-
(5.76)
Bent, H. A. Chrm. Rn. 1961, 61. 275-3tl.

Aci4iay, basicity, and oahco- chemical propenies depend on other fac.ION in Gdclilion 10 electronqati\'ity. Nevcnheless, varialion in dectroneptiviay is important in determinina these
P"Opcrties .
.,. Sec Footnote 38.

40
41
Strcitwieser. A .. Jr.; Ziegler. G. R.; Mowery. P. C.: Lewis, A.; Lawler, R. G. J . Jim. Chrm. S.
'"'
13S7-13.58.
Marl\gra(. J. H.; Kau. R. J. J . Org. C1trm. 1972, 17. 7t7-718.
Electronegat ivity
193
H,
H,
Fig. 5.33 Biphenylene. Shaded orllitals ha"C increased p character; hence un$hnded ortJ;tal
has increased s chlltllCtcr, increased electroneptivity. (From Streitwieser, A .. Jr. ; Ziegler.
G. R.; Mowry, P. C.; Lewis, A.; uwlcr, R. 0 . J. Am. Cltem. Soc. 1968, 90, J3S7-13.59.
Reproduced with permission.I
Although tbe products differ considerubly in these two reactions, presumably the
mechanisms are not drastically differenL The negative hydroxide ion artacks the most
positive atom in the organic iodide. In methyl iodide this is the carbon atom (X1 > Xcl
and t he iodide ion is displaced. In the triftuoromethyl
the ftuorine atoms induce
a positive charge on the carbon which increases its electrenegativity until it is greater
than thai of iodine and thus induces a positive charge on the iodine. The latter is thus
attacked by the hydroxide ion with the formation of hypoiodous acid, which then loses
an H+ in the alkaline medium to form 10-.
It may seem paradoxical thallhe carbon atom can induce a greater posilive chaq:e
on the iodine than that which the carbon itself bears but a simple cak:ulation based On
electronegativity equalization (see pages 198- 199) indicates Ihat the charges
=
+0.21, <'lc = +O. IS, and 6p -0. 12. Althouch it is exceedingly unlikely thatthe real
charges have Jhese exact values, they IU'e probably qualitativrly accurate. This is an
example of the importance of the ability of an atom to donate or accept charge. Iodine
is the most polarizable atom in this molecule. The large, son. polarizable nat ure of the
iodine atom allows it to accept the larger char&e.
A similar reaction or more iruerest to inorganic chemists is the react ion between
carbonylate anions and Dlkyl iodides:
CHJI + Na(Mn!COisl- ---+ Nal + CHJMn(C0)3
2CFJI + Na(Mn(CO),r--+ Nul + CzF,. + Mn<CO),I
(5.77)
(5.78)
In this reaction also, the polarity of the C- 1 bond depends upon the substituenls on
the carbon atom .
It is an interesting paradox that most of the example.s of variable electronegativity
come from organic chemistry, although it is probable that electronegativity varialion is
much more important in inoraanic chemistry. For example. there must be a large
difference in electronegativity between d1spl Cr(lll ) in (Cr(NH1 )6 J1 + and spl Cr(V I) in
CrO! . The fact that it is not so well documented as yet speaks to the difficulties of
treating the electronegativities of transition metals. Some examples that will be
discussed include the basicity of N HJ versus N F1 , the oxidation slate of oxyacids, the
tendency of metals to hydrolyze, and the effect of ring strain on basicity (Chapter 9).
Pa uling's
Bedt-onegativity
Pauling observed that bonds between dissimilar atoms were almost always stronger
than might have been expected from Jhe strength of bonds of the same dements when
bonded in homonuclear (nonpolar) bonds. For example. the bond energy of chlorine
194
5 Bonding Models in tnorgonic Chemistry: 2. ne Covolent lone!
monolluoride. CIF, is about 2SS kJ mol- 1 greater than that ofeitherCI 2 (242 kJ mol- 1)
or F, ( 158 kJ mol- 1) . Pauling suggested that molecules formed from atoms of different
t'flf!rgy resulting from resoclec.rronegativity would be stabilized by ionic
nance of the sort:
(5.79)
For molecules in which atoms A and Bare identical. b c <<a (see page 141 for the
H.. molecule). and the contribution of the ionic structures is small . If B is more
than A , then the energy of the contributing structure A B- approaches more nearly that of the purely covalent struciUre A- B and resonance is
enhanced. On the orher hand. the energy of s+ A - is so prohibitively high that this
structure may be dismissed from funher consideration. For a predominantly covalent.
but polar, bond. a > b >> c. The greater the contribution of the ionic structure (i.e .
the closer it comes to being equivalent in energy to the covalent structure ) the greater
the resonance bet ween the contributing st ructures and the greater the stabilizing
resonance energy. Pauling suggested that electroneglltivity could be estimated from
calculations involving this ionic resonDnct enefJY. The interested r-eader is referred to
Pauling's discussions of the subject for the details of the methods he
but an
outline follows.
Pauling assumed that if the CIF bond were completely covalent , its bond energy
would be simply the averaae of the 0 2 and F 2 bond ener-gies:
242 + 158 "' 200 kJ mor-

2
(5.80)
The ionic resonance energy is the difference between the experimental bond energy of
OF, 255 kJ mol- 1 , and the calculated value. 200 kJ mor - , or S5 kJ mol- 1 Pauling
defined ohe difference in electronegativity between chlorine and ftuorine as the square
root of the ionic resonance energy ...,
f5S
V%.5
o.76
(5.81)
This may be compared with the oabular vulue for the difference in electroneg:uivities
of fluorine :ond chlorine. 3.9H - l . t6 "' U.82. which is bllsed on many experimental
duta. nor just the single calculation illustrated here. Once again. the details of the
calculation are not panicular!y imponunt since Pauling's method of obtaining elcc
tronegativity data is prohubly mainly of historical
The concept of
resonance is still quite useful. however. Unfortunately, as alternative
methods of treating elec tronegativity have developed. the fact that a bond with panial
ionic character can be stronger than either o purely covalent or purely ionic bond has
often been overlooked. Energies associated with dectronegativity differences can be
useful in accounting for the tooal bonding enefiies of molecules.
Other Methods of
Estimating
Electronegotivity
Many other methods have been suggested for determinina the electronegativity values
of the elements. Only one general method will be discussed here. It is to consider
electronegativity to be some function of size and cllarge. These methods differ among
c f'oulinl. L 1M Noturr of tltr Clotmirfll Bond. ltd!. : Corrdl Univenily: Ithaca. NY. t960;
0,....3 .
., llle convenm ractor96.S kJ
Is included because
up his scale bnsed on bond
cnorgies measured in etccoron volts.
Not all
would qru with
$lillemcnl.
Eleetronegotivity
195
themselves only in the choice of function (energy. force . etc .) and the met hod of
estimating the elfecrive charge. Allred and Rochow'' defined electronegarivity as the
electrostatic/Met' exened by the nucleus on the valence electrons. They used effective nuclear charges obtained from Slater's rules46 and obtained the formula:
XAR
= (3.590 Z*/r2)
+ 0.744
(S.BZ)
where r is the covalent radius (pm). The Allred-Rochow scale has been widely
accepted as an alternative 10 Pauling's thermochemical method for determining electronegativities. Allred-Rochow values are listed in Table .5.6.
Another delinirion that is based on size and charae. bur in a unique way, is the
definition of Sanderson., which is based on relative electron density. This method has
never been acce pted widely, alrhough Sanderson has applied i1 successfully 10 a
variety of problems,.a and his values were the tlrsr to illustrate the in1eresting electronegativiry properties of the posllransition elements (see Chllprer 18).
Choice of
Electronegativity
System
Choice of Hybrids
for Nonmetals
Values for each of the electronegativity sysrems discussed here are listed in Table .5.6.
With more than one valid system available, the choice of the "best" one is not always
easy. We can arbitrarily divide the various methods into two groups. One consists of
the methods that depend on orbital energies: the
theory, density
funclional rheory, and the spectroscopic theory. They may be termed " theoretical" or
"a.bsolu1e" scales because they ace based only on the fundamental orbital energies of
isolated atoms. The other scales are "empi rical" and "relative" because 1hey utilize
experimentally oblained data such as enthalpies offormation. covulcnt radii. etc. Bolh
groups of systems have advantages. In general, the energy scales are more satisfying
because they are. in a sense. more fundarnemal and basic. The empirical methods also
have an advantage, resullillll directly from their methods of derivation. In orher
words. variables such as hybridiwtion, etc.. are often "built in" as long as the atom
under considera1ion is in a fairly typical environment . Each of the empirical methods
advantages and disadvantages, adherents and detrac,t ors, and they do not really
differ greatly among themselves. If the situation is sufficiently nonspecific to make it
necessary to use an empirical system, it probably will not make a greBJ deal of difference which is chosen. However, one must be consistent and avoid picking the value
for one elemem from Pauling. another from Allen. and a third from Allred-Rochow.
By judicioos mixing of systems like this, one could probnbly " )lC'ove"
Choosing the appropriate hybridiwion for use with
elcctronegativities
5ometimcs presents problems. Only the elements to the left in the periodic table have
unambiguous hybridiwtion
by structure. Thus few would argue with an
assumption of sP: for boron in its tricovalent compounds, and organic chemistry is
based on the successful assumption of digonaJ (sp), trigonal (spl), and tetrahedral (spl)
hybridizations for carbon. However. the hybridizations of nilrogen, oxygen, phos
s Allred, A . L.; Rochow, E. G. J. IM'II Nw:l. Chtm. ttsl. S. 164-268

... Alred :mel Rochow c:ounled all o/lhe eleclrons in a partica4ar 11om as
lhe dcctron coming
rrom ano&her alan. so their Z. values are O.lS hi&f1et lhan lhosc ot>lained by 1hc: usual :IA>fication of
Slalcr' s rules. Such differences are unimpertaru as tona as one is eonsistenl in I he
T1ley
wil
illlo lhe
ror fllllna Eq. S.82.
., Sanderson, R. T. J. Ch..,, due. t95Z, 29. Sl9- S..; tt54. J/. 2- 7 .

.. Sanderson. R. T. l'ol4r
Kriqer: Malabar. FL. t!ll9,
Academic: New YO<t. t98); Simp"
Slllurancn;
196
5 Bonding Models in Inorganic Ch-istry: 2. The Covalent Bond
phorus, and sulfur do not fit well into such simple schemes. This is because the
hybrids are often some nonintegral mix of s and p character. Methods have been
proposed for determining hybridizations from bond angles, but they are approximate
at best (see O.apter 6). Recently. Bratschll has suggested a purely numerical rule
based on an extension of the hybrid properties of the ear1y, well behaved e.lements in
each row. Elements with group numbers, N I (l A , 1), 2 (liA, 2), 3 (IliA, 13), and 4
(IVA, 14) form hybrids of the type spN - 1. For the nonmetals to the right of the
periodic table, Bratsch suggests working hybridizations of nitrogen, Group VA (IS)
sp 20".4 s character; oxygen, Group VIA (16) sp' = 17",4 s character, etc. These
values are in reasonable agreement with estimates from bond angles, and the electronegativity values thus obtained are consistent with electronegativities obtained by
other methods. These values have been listed in Table S.6, but other hybridizations
are listed as well. A value of 20",4 s character might be best for nitrogen in ammonia,
but in the ammonium ion, the nitrogen atom is isoelectronic with the carbon in
methane, and the hybridization must be spl.
GI'Oup
Electronegotivity
It is often convenient to have an estimate of the Ulductive abtlity of a substituent

group. As we have seen previously, we cannot use a single value of carbon (-2.5) to
represent the electronegalivity of carbon in both CH1 and CF1 The electronegalivity
of these two groups will be
of carbon as it is
by the
of thue hydrogen OF
atoms. Estimation of group electronegativities has been approac.hcd from a variety or ways. Organic chemists have developed
sets of subslituent constants from kinetic data50 and these have proven useful in
certain inorganic systems as well. Other values have been obtained from physical
measuremell(s of electronic effects, and calculated directly from atomic electronegalivities." Some comparative values are listed in Table S.7. We need not go into the
details of the various methods, but note that there is general agreement , and that two
s imple rules-of-thumb hold for group electronegat ivilies: (I) The inherent group electronegalivity, De is approximated by the simple average of the inhe.r ent atomic
electronegativilies. (2) The charge coefficient , b 0 , is an average as well, bu t
proportional to
number of atoms in
group. Thus the electronegallvity of a
group is given by:
(5.83)
II is intuitively reasonable thatlhese values shou ld be un average over then values of

the rlh.... nth atom. In the same way, the charge coefficient should be inversely
proportional (i.e. the charge capacity should be directly proportiona() to the number.
n, of atoms over which the charge may be spread. This is
most important proputy
ofgroup
amount of
Groups are "supuatoms"

or
of absorbi11g a large
This means that groups can donate or accept
., Bratsdl. S. G. J . Clwm. E:duc. 1!111. 6$,

,.For a review or \'&rious :sets o( subsliluenl COIISIAIIIS, see Lowry, T. H.; Ricllarc!.soft, K. S.
MuhDnism onJ
in Organic Oo' mhlf], :lrd ed.; Harper & Row: New Yotlc, 1987:
A> tS2-IS8.
" for melllods or caleulolina 1f0UP decttonep&ivilies from Mutlilten-Jall't dec:lrOnqalivity values
of the C()IISUIIknl :uoms. see Bruseh, S. G. J. Chmr. due:. ttiS, 62, IOI- t03.
Electronegotivity
197
Talole 5.7
xo
Clio
ho
Exp.rim.......
wat-
xc
Group
scale
leV)
IVl
scale
CHl
2.31
2.30
2.32
7.44
7.4S
7.48
7.52
12.8.5
/0.50
10.24
10.12
10.68
l o.62
12.09
11.8J
8.10
8.92
13.16
11.89
9.61
/0.80
8.30
9.90
3.11
2.34
Esflmo'" .......
--groups
Colculated volws
.tectronegalivities of
Paoiling
CH.1CH1
CF1
CCI,
COOH
CN
NH:
NF2
OH
OCH1
2J2
3.47
3J2
2.95
3 .19
3.04
3.36
3.32
3.76
2.47
2.78
3.$3
3.18
2.82
3.42
2.52
3 .12
Pauling
4.64
1.77
3.58
3.90
5 .32
2.88
4.33
3.41
S.43
6.23
6.47
4.31
5 .92
S.JI
6 .11
7.02
8.86
2.S9
5 .74
3.3S
3.03
2.8-J.S
3.3
1.7- 3.4<
2.3-3.9<
Cslc:ulaled by
or deciiOnc...livily
Two
valueo are given to indicate variation. Roman valueo an: from
Bntseh, S. Ci. J . Chnn.
191&. 6.S. 2U-ZZ7. I
values
are from Waus. J. C., Ph.D. Dissertation, Uoivcrsity of
Maryland, Colleac Park, 19'11. See elso Footnote b.
Various experimental mclhods. mos1ty infrated spectroscopy.
For details, see Huhecy, J. E . J . 1'h1 Chrm.
69,
3284-329 1.
The wide ranac of values reouiiS from Ihe possibilily of

conjuptlon of lone pair of 1r electrons wilh the remaindet" of
Jhc molecule.
charge better than would be indicaled by their inherent electronegativilies (a values)

alone. For example, the methyl group is slighlly , though not significantly, more
electronegaJive than hyd rogen. Yelthe merhyl group is generally considered a better
donor than is the hydrogen atom . It is the grealer charge capacit y, which results from
the ability 10 spread the charge around lhat allows lhe methyl group to donate more
electron density than the smaller hydrocen alom:
1'8
5 Bonding Models fn Inorganic O.oonistry: 2. The Covolenl Bond
Methods of
Estimating Charges:
Electronegativity
Equoli:z:ation
FOC" many reasons. chemists would like to be able to estimate the charges on the
constituent atoms in a molecule. There have been many attempts to do this, but none
has proved to be completely successful. The ideal way would be to solve the wave
equation for a molecule without the use of any simplifying assumptions, and then to
calculate the electron distribution. Such ab initio calculations are possible for small
moleculesSl but become
difficult as the number of atoms increases. Even
when the calculations are possible, there is not complete agreement among chemists
as to the best way of apportioning the charge density among the atoms in the
molecule .H
Several workers have suggested semiempiricaJ methods based on electronegativity for the estimation of charge. Only one method will be discussed here.
has proposed thai when a bond forms between two atoms electron
density will shin from one atom to I he other until the electronegativities have become
equalized. Initially the more electronegative element will have a greater llllraction for
electrons (Fig . .5.34), but as the electron density shifts toward that atom it will become
negative and tent! to attract electrons Jess. Conversely. the atom which is losing
electrons becomes somewhat positive and artracts electrons beuer than it did when
neutral. This process will continue until the two atoms auract the electrons equally. at
which point the electronegativities will have been equalized and charge transfer will
cease (Fig. S .3.5):
XA - "A
+ bA6A
= Xe
= ue -
(5.84)
be6A
(5.85)
bA + be
B
A
B
(bl
(aJ
Fog. 5.34 Relation between ionizaaion energy-declron affinity curve (solid line) and inherent
etecrronegaaivily (dashed line) for a less elcclronegalive element (A) and a more
e leclrOfleBalive demelll
(8).
" Figures 5. 14-5.t8 were oblained from suc.h caleulalions.

"PoliU:er. P.; Re8DO. P. H. J . Am. Clwm. Soc. l91l. 'H, 8308-8311. Evans. R. S.; Huhccy, J. E.
Chtm. l'hys. Lttt. 1973. 19. 114-116.
,_.Sanderson. R. T. J . Chtm. Educ. 1954, Jt. 2-7. See also FoolnOie 48.
Electronegativity
199
Fig. 5.35 Supaposition d

ionizatioo energy-dectron
affinity curves for a more
electronegative (B) and less
electronegative (A) element.
The common
(a
equalized electronegativity)
is aiven by the dashed line.
The partial charges in the HCI molecule may be estimated with Eq. 5.8.5 by using
the appropriate a and b values from Table 5.6: aH = 7. 17. bH = 12.84. aCI(l4'l' =
12. 1.5. and bc114,-._,1 = 11..55.
= 12.15 - 7. 17 = +0 20
I I.SS + 12.84
.
(5.86)
The charge estimated by this method is often different from a similar estimate based on
dipole moments. tflhe total ionization energy (including the electron affinity) were the
only energy involved in the charge distribution. Eq . .5.85 would be rigo.-ously con-ect.
In a molecule. however. Olher energy terms are important . The exchange energy
associated with the overlap of orbitals will be reduced if the charge lransfer is too
great. The Madelung energy (so named because of resemblance to !hal found in ionic
crystals) resulting from the electrostatic auraction of A .. for
(within the molecule)
tends to increase ionicity. These energies tend to ca ncel each other in effect because
they work in opposite directions . so Eq. 5 .85 can be considered a useful. qualitative
approximation.
Allhough there is no universal agreement on the .. real .. charges in molecules.
various auempts have been rrodc to improve upon simple eleclronegarivity calculations. One method is to estimate the exchange and Madelung energies by simple
bonding models. and then to use them to adjust the values obtained by the electronegativity equalization mel hod. This modification has been found to correlate well
with some ab initio calcularions for some simple molecules.H
There is a maxim thal when there are many treatments for a disease. none of them
is completely adequate. This same idea could be applied to electronegarivity in view of
the many attempts to define and qua ntify it. Nevertheless. bond energies. polarities.
and the inductive effect are fundamental to much of inorganic. organic. and physical
chemistry. hence the efforts applied to electronegativity theory. While there is as yet
no complete agreement on all aspects of electronegalivity, defining it some way in
terms of the energetics of the valence electrons is generally accepted as the best
approach. although the last word has undoubtedly not yet been said on the matter.
a-
200
Slondin11 Mod-'s in lnorgonic Chemistrr. 2. Tlte Covolent lond
Problemc
5. 1
Draw Lewis structures for CS2 , PF1 , SnH4 , HONH2
5.2 Draw Lewis structures ror H2C0 1 , HN01 NO. Be(CH1h.

S.J Draw Lewis structun:s for BF1, SFo. XeF2. PF,, IF,.
5.4 Show that there is no mismatch of the sian of the wave function in the ., system of (PNC!z}4
in contrast to (PNC!VJ.
5.5 Write the MO electron conligur.uion for the NO- ion.
a. What it the bond order?

b. Will the bond length be shorter or lonaer than in NO?
c. How many unpaired electrons will be present'/
d. Will the unpaired electrons be concentr.<ted mon: on the N
or the 0? Explain.
o;
5.li Consider the hypochelic:al dioxyaen superoxide.

o;. discussed in Chapter 4. If this
compound did exist, what would be the eleclronic structures of the ions? Discuss bond
orders. bond lengtha, and unpaired electrons.
5.7 The resonanoe of BF1 (pqe 145) is stat a mauer of some dispute becaiJ.se one chemist will
point to the double bond in Slruotun: II (favat:lbly); another will point to ,-. (unfalf<nbly).
Suggest a molecule for which clwJes completely rule out resonance.
includina formal charaes. for 0 1 , SO,. NO,.
5.ll Write resonance
5.9 The assumption was made that the carbon-catbon u bond in CH, -CH: is
in C H1CH1 . In reality, it is probably JOmewhac stronaer. Uiscuss.
as !bat
S. IO The NNO molecule was discussed on paae 14S. Consider the isomcnc NON molecule.
Would you expect it to be more stable or less stable: than NNO? Why? Why does CO: have
the OCO
rather than COO?
5.11 The cyanate ion, OCN -. forms a stable: series ofsahs. bw many fulminates. CNo- . are
explosive (L. fu/mino, to flash). ExplAin. (For a lead. see pa&e 14$; for a
different
approac.h , sec Pauling, L . J . Ch,m.
1975, $2. $77.)
5.12 Calculate the c:lc:ccronc:aalivicy of hydrogen from the ionization potential and the electron
affinity.
S.U In later chapters you will lind examples ot I he
of covalent bonds throuah ionic

resonance c:ne.rgy. For now, show its importance by predictina whelher the molecules NX1
(X
hydrogen or halogen) are slable. that is, whether the reaction
N2 + JX: -
2NX,
is exothermic. Assume thai neither ammonia nor any or the nitrogen

has yet been
synthesized. so you are permitted to look up bond enerai for N& N, N-N. and X-X
(Appendix El. but you must predict the bond eneray ot N- X.
5. 14 Which do you expect to be more acidic:
II
I
CH -P-OH
'
or
o-OH?
CH 1
Explain. (Sec: Cook, A. G.; Mason, G. W. J. Or,. Clwm. 1972, 17, J:J42-JJ4S.)
5.15 In Table 5.6 the dc:clr'Onc:plivitia of the noble aasc:s are, as aroup, the
hi&hest known.
Probl-
201
being higher even than hose of the halo&cns. Yet we all know Jhal the noble gases do not
accept elecl rons from elements of low electroneaativily:
Na +A--+ NaADiscuss Jhe meaning of the elect roneptivhies of I he noble aases.
5.16 In ruscussing iOctic resonance, AB ... Ae-, where:
1/1 :
ar/lwv
+ b</1-.,
x,.
Pau6ng assumed that "'-made a negliaible contribution if

Xe The bond energy of
Cl, is 240 kJ rnoJ- and the bond length is 199 pm. In the Cl 2 molecule. x,.!!Xe Show by
means of a Bom-Haber typc calculation that the canonical Slructure, ctct-. cannot
contribute appreciably to the stability of the molecule. (You may check your answer with
Pauling, L T11r Natu,. ofthr ChrmicoJ Bolld, 3rd cd. ; Cornel University: Ithaca, NY,
1960; p 73.)
5.11 The energy necessary to break a bond is not always constant from molecUle to molecule.
For example:
NO, --+ NC!t

ONCI --+ NO
Sugesla
+0
Cl
Mf - 37S kJ mol- 1
Mf ISS kJ mol- l
reason for Jhe difference of - 200 kJ
mol- between these two enthalpes.
5.18 From what you know of the rdationship between ionization cne<Jies, dectron affinities.
and electroncpJivitics. would you expect the addilion of some d chaJKter to a hybrid to
rnise or lower the elearonc&JIIivily; for cum pie, wid sulflw be more electroneplive when
hybridized
or sp>dl?
5. 19 The dipole momem of H-CaC-CI is in the direction-. Explain.
5.10 The leaend 10 Fla. S.ZO says "The lu and 3v MOs arc essentiay nonbonding. " Dncribe
these nonbondina orbitals more explicitly, perhaps in VB terms.
5.21 Look at Figs. 5. 14 and S.IS caref\Jtl y. Identify:
a. the nodal planes responsible for lhe symme.try or 1he MOs (i.e., sjsma, pi, e.t c.).
b. any changes in elec1ron density that you can ascribe to bonding versus amibonding
situations.
5.22 Oxygen is more e lectronq;3tive than carbon and
S. llln indicates that there is more
electron density on oxygen than on
in carbon monoKid e. Yet t he dipole moment of
CO is quite
(0.373 x 10 - "' C m; 0. 112 0) and it is known thai thr oxygrn atom is thr
posltir rnd of thr dipolr! EKplain. Hint: Does a compArison with the isoelectronic
din itrogen molecule (Fig.. S. l8b) help?
5..23 Using the MO treatment of Bc H1 (page 175)
for the molecular orbitals in CO,.
u a Slartina point , write linear combinations
5.24 Construct a molecular orbital di-.ram for water using the proper character table and
deriving reducible representations. The Lewis s tructure for water suagcsts two equivalent
nonbondina and two equivalent bonding pairs or electrons. but your molecular orbital
ruagram should show four nonequivalenl molecular orbillls. How can you rationalize ahis
djlferencc? Which molecular orbit :lis do you think best represent the two nonbondina pain
and the bondintl pairs? Compare your rcsuh wi1h that found In Shustorovich, S.; Dobosh,
P. A. J. Am. Chrm. Soc. 19?9, /OJ, 4090.
5.25 The HOMO (o 1) of NOi' is somewhat an6bondifla. On this basis, what predictions would
you make about the N-o bond lengths In NO;, NO,, and NC>;? How many unpaired
202
S Bo,ding Modell in lnorgonie Ch-iltry: 2. The Cowolent Bond
dectrons would each of these three species have? Would you expeCt the OOO>bondins
dectron pairs on nitrogen or those on oxyacn to be more reactive? Explain.
5.26 Co..struct a qUalitative molecular orbilal diql'lllll for
presented in Figure .5.31 for NOi' .
al>d compare it to the one
5.1:7 Return to Problem 2.25. Answer it now in terms of group electronegativity.

5.28 The methyl group is usually considered to be electron.Oonatin.11 with regard to hydrogen.
yet its e.lectronegativity is nor lower than hydrogen but slightly higher. Explain. (Hinr:
Think specifically about situations in which the methyl croup is a good donor.)
5.29 You may have learned in organic chemistry that the acidity of acids R-c{O)()H depends
upon XR Discuss in terms of R H. CH,. and CCI, .
5.30 The F,SeO group Is extreme.ly electronegative. On the basis of the ' H N MR c.hemical shills
.5.36) of methyl compounds. CH,X.
ond Scppclt hnve
that this group
may be evezr more electronegutive than ftuorine. Ois<U$S.
4.0
S 6tppm TMSJ
C'hcmicoJ $hln
Fig. 5.36 [Translated from the original paper. I Correlation of the 'H chemical shill or methyl
compounds CH,X with the electroncaativity
of the group X . Extrapolation
to the OSeF, group gives an electronegativity sliahtly areater thon that d fluorine. !From
Huppmonn. P. : Lentz, D. ; Scppelt, K. Z. AnOr/1. MI. Chrm . 1981,471. 26-32. Reproduced
with permission.!
Chapter
6
The Structure and
Reactivity of Molecules
The Structure
of Molecules
In this chapl:er a few simple rules for predicting molecular sl.r uctures will be investipled. We shall examine lin! the 110/tnct shtll tltctron pair rtpulsion (VSEPR)
model, and then a purely molecular ortlital trearmenl.
Valence Shell
Electron Pair
Re pulsion Theory1
We begin by considering the simplest molecules-those in which the electrons on the

cenlral atom are all involved in bonds. It should be kepi in mind that each molecule is
several energy factors and that the
a unique structure resulting from the interplay
following rules can o nly be a crude attempt to average the various forces.
or
I. First, from the electronic configurarion of the elements, detennine a reasonable Lewis struaure . For example,ln lhe carton dioxide molecule, there will
be a local of 16 valence electrons to distribute among three utoms:
:o::c::o:
or
:o::c
:o:
(b)
(a)
Note that a Lewis struCture says nothing about Ihe bond angles in the molecule
since both (a) and (b) meet aU the criteria for a valid Lewis st ructure.
2. A structure should now be considered which lets all the electron pairs in the
valence shell the cenlral atom(s) gel as far away from each other as possible.
In the usual tT-'fT treatment this usually means ignoring t he '"bonds temporarily
since they will follow the o- bonds. In carbon dioxide there will be lwo o- bonds
or
' Gilespie. R. J. Ch,m. Soc. R,.;. ltn. 21.

Mokador Crl<NMtry; AJya and s-: Boslon. 1991.
R. J .; Harptlai. I. Tlw VSEI'R Modd of
203
204
6 The Structure and Reactivity af Molecules
and no nonbonding eleclrons on the carbon atom. and so the preferred orienta.
lion is for I he u bonds to form on opposite sides of lhe carbon atom. This witl
require hybridization of the carbon 2s and 2p< orbilals to form a digonal hybrid,
with a bond angle of 180".
3. Once the struaure of the u-bonded molecule has been determined, w bonds
may be added as necessary to complete the molecule. In carbon dioxide. the Px
and Py orbitals on the carbon atom were unused by the u system and are
available for the formation of w bonds. A complete structure for carbon dioxide
6. la.
would thus be as shown in
These simplified VSEPR rules may seem a far cry from the more elegant application of symmetry and molecular orbitals to the beryllium hydride molecule and the
nitrite ion (Chapter .5), or the BH. molecule (Problem 6.27). Although the molecular
orbital approach can rationalize these structures. the direct application of the VSEPR
rules is by far the easier way to approach a new structure.
(
0
) (
+
(-----=-->---)
D.,
,.,
IaI
120'/ at, (
H,c-L.:_
) _..........-a
c
'\..at,
o..
c,.
(bl
(cl
I hi
F"I!J. 6.1 Some simple molecular Slructures in which all electrons on the central a10m form
bonding pllirs: (a) carbon dioxide, wilh two sp u bonds (solid lines) and two w bonds;
(b) trimethylborane. with 1hree sp' u bonds; (c) carbonyl chklride (phosgene). with three
spl u bonds and one C-0 w bond; (d) phosphorus oxylluoride. with four approximately
sp' 17 bonds plus one p-d .,. bond; (e) phosphorus pentalluoride, with five sp)d 17 bonds;
(f) sulfur lw:xafluooide. wilh six spld1 u bonds; (g) ammonium tetralluorobonte; each ion has
four sp> u bonds; (h) aloolinum brO<Nde dimcr.
n.. Structure of Molecules
205
Trimethylborane (DM).2 We may assume that the methyl groups will have
their usual configuration found in oraanic compounds. The Lewis structure c:l
will place six electrons in the valence shell of the bor-on atom, and in
order that the-electron pairs be as fair apart as possible, lhe methyl groups should
be located at the comers of an equilateral triangle. This results in spZ, or trigonal
(tr), hybridiZlUion for the boron atom (Fig. 6. 1b).
Phosgene (C1 ,.). A Lewis structure for OC0 1 has eight electrons about the
carbon, but one pair forms the .,. bond of the double bond, so again an spZ, or
trigonal, hybridization will be the most stable (Fig. 6. lc).
Phosplrorus o;zyftuoride (C,,.). Two Lewis structures can be drawn for the
OPF, molecule.
: F:
:F:
:o::P:F: ......... :Q:p:f:
:F:
:F:
(a)
(b)
To a first approltimation, the three fluorine atoms and the single oxygen atom will
be bonded to the phosphorus atom with a bonds from spl tetrahedral orbitals. One
of the live ldortlitals on the phosphorus atom also can overlap with a 2porbital on
the oltygen atom (Fig. 6. ld) and fonn a fifth bond, d.,-p.,, funller stabilizing the
molecule.
Phosphorus penlajluoride (DM> A Lewis structure fur the PF5 molecule
requires len electrons in the valence sheU of the phosphorus atom and the use c:l
ls, Jp, and 3d orbitals and live u bonds. II is impossible to form five bonds in three
dimensions such that they are all equidistant from one another, but the trigonal
bipyramidal (Fig. 6. le) and square pyramidal arrangements tend to minimize
repulsions. Almost every live-<:oordinate molecule (coordination compounds excepted) which has been carefully investigated has been found to have a trigonal
bipyramidal structure. The structure of the PF, molecule is shown in Fig. 6.le
(splJ hybrid). The bonds are of two types: axial, the linear F- P-F system: and
equatorial, the three P-F bonds forming a trigonal plane.
Sulfur hexafluoride (OA> Six sulfur-fluorine u bonds require 12 electrons in
the nlence shell. Six equivalent bonds require an cx:tahedron and so sulfur will be
hybridized splJZ as shown in Fig. 6. lf.
Ammonium tetroftuoroborale (Td> Both the ammonium (NHt> and
tetrafluoroborate (Br.) ions are isoelectronic with the methane molecule and we
might therefore reasonably expect them to have similar structures. Indeed, all
four bonds are equivalent, and since the electrons avoid each other as much as
possible, the most stable arrangement is a te1r11hedron (Fig. 6.18).
Aluminum bromide (l>v,). For the molecule AIBr,, a structure similar to
that of trimethylborane would be expected wilh 120" bond angles. Experimentally. however, it is found that aluminum bromide is a dimer,
This is
readily explainable as a result of lhe tendency to maximize the number c:l bonds
formed since AI2 Br6 contain5 four bonds per aluminum atom. This is possible
The poin1 poup symmdry d each molecule Is ,iven in paretllllc:ses. Sec Chapter ) .
206
6 T11e Strudwe and Reacti.Hty of Molecules
because the aluminum atom can accept an additional pair of electrons (lewis
acid, see O!apt.er 9) in its unused p orbitul and reh)lbridize from spl to spl. We
should expect lhe bond angles about the aluminum to be approximately
tetrahedral except for the strain invo lved in lhe AI- Br- AI- Br four-membered
ring. Since the average bond angle within the ring must be 90", we might expect
bolh the aluminum and bromine atoms to use orbitals which are essentially purely
pin character for the ring in order to reduce lhe strain. The structure oflhe AI 2Br6
molecule is shown in Fig. 6. 1h.
Although lhe discussions of the preceding molecules have been couched in valence
bond terms (Lewis structures. h)lbridiz.adon. etc.), recall !hat the criterion for molecular shape (rule 2 above) was lhat the u bonds of lhe central atom should be allowed to
get as far from each other as possible: 2 at 180". 3 at 120", 4 at 109.5", etc. This is the
heart of lhe VSEPR melhod of predicting molecular structures, and is, indeed.
independent of valence bond hybridiz.ation schemes, although it is most readily
applied in a VB context.
1be source of the repulsions that maximize bond angles is not completely clear.
For molecules such as
B(CH 3) 3 , or O- PF3 we might suppose lhat van der
Waals repulsions (analogous to the Born repulsions in ionic crystals, Chapter 4)
among. for example, the three me thyl groups mi&ht open the bond angles to lhe
maximum possible value of 120". In the next section we shall see lllat nonbonding
pairs of electrons (lone pairs) are at least as effective as bonding pairs (or bonded
groups) in repulsion. and so attention focuses on lhe electron pairs lhemselves.
Although a number of lheories have been advanced. the consensus seems to be lhat
the physical force behind VSEPR is lhe Pauli force: Two dtrons of the same spin
CtJI!II()t occupy the same space. However, it should be noted that there has been some
d isagreement over the matter. Nevenheless, as we shall see, lhe VSEPR model is an
extremely powerful one for predicting molecular st ructures.
Structures of
Molecules
Containing
l one Pairs
of Electrons
When we investigate molecules containing lone (unshared) elect ron pairs. we must
take into account the differences between the bonding electrons and the nonbonding
electrons. First, before considering hybridiuuion and the energies implicit in the
bonding rules (ChapterS) let us consider the simplest possible viewpoint . Consider the
water molecule in which the oxygen atom has a ground Mate electron configuration of
The unpaired electrons in the P, and Py orbitals may now be paired
wilh electrons on two hydrogen atoms to give H10 . Since the p1 and p1 orbitals lie at
right angles to one anolher. maximum overlap is obtained with an H-0-H bond
angle of 90". The experimentally observed bond angle in water is. however. about
104!". much closer to a tetrahedral angle. Inclusion of repulsion of positive charges on
!he adjacent hydrogen atoms (resulling from the fact that the oxygen does not share
!he electrons equally with the hydrogens) might cause the bond angle to open up
somewhat , but cannot account for the large deviation from 90". Not only must the
H-H repulsions be taken into consideration, but also every other energetic interaction
in the molecule: all repulsions and all dumees in bond energies as a function of angle
and hybridization. II is impossible t.o treat this problem in a rigorous way, mainly as a
resuh of our ignorance of lhe magn itude of lhe various energies involved; however,
certain empirical rules have been formulated.
first, as we have seen in examples on the previous pages, bond angles in
molecules tend to open up as much as possible as a resull of the repulsions between
the electrons bonding the substituents to the central atoms. Repulsions between
The Structure of Mole cule s
2 07
unshared electrons on the central atom and other unshared electrons or bonding
electrons will affecr the geometry. In fact . it is found that the repulsions between lone
pair electrons are greater than those between the bonding electrons. The order of
repulsive energies is lone pair-lone pair > lone pair-bonding pair > bonding
pair-bond ing pair.J This results from the absence of a second nucleus at the distal end
of the lone pair which would tend to localize the electron cloud in the region between
the nuclei. Because the lone pair does not have this second nucleus. it is aurae ted o nly
by its own nucleus and tends to occupy a greater t1111.111lur volume (Fig. 6.:!).
The difference in spatial requirements between lone pairs and bonding pairs may
perhaps be seen most clearly from the following example. Consider an atom or ion
F- , orNe
Assume
with a noble gas configuration such as C'- , N)-,
that the eight electrons in the outer shell occupy four equivalent tetrnhedral orbitals.
Now let a proton interact with one pair of electrons to form an x- H bond (Hcl-,
NH 2 - , OH-, HF. NeH). The proton will polarize the pair of electrons to which it
a ttaches in the same way that a proton or other small. positive ion polarizes an anion
(Fajans' rules . Chapter 41. Electron density will be removed from the vicinity of the
nucleus of the first atom and auracted toward the hydro,en nucleus. The remaining.
nonbonding pairs may thus expand at the expense of the bonding pair. Addition a
second proton produces two polarized, bondin, pairs and two expanded lone pairs
H,N-, H, O.
A third proton forms H3C - , NH 3, and H30+ with one
lane pak_ A f00nh proton produces CH 4 and NH; in which all four pairs
electrons have been polarized toward the hydrogen nuclei. are once more equivalent,
and hence d irected at tetrahedral angles.
From this point of view, the water molecule can be considered to be hybridized
tetrahedrally to a first a pproximation. Since the two lone pairs wilt occupy a greater
angular volume than the two bonding pairs. the angle between the latter two is reduced
somewhat (from 1094 to 10411. allowine the angle between the lone pairs to open up
slightly. The series methane, CH 4 (no lone pairs, bond ungle Jfl9!1; ammonia, NH3
(one lone pair. bond angle .. 101"): and water, H 20 (two lone pairs, bond angle =
1(14!") illusm1tes an isoelectronic series in which 1he increasing requirements of the
nonbonding puirs reduce t he bond angle (Fig. 6.3).
or
or
Fig. 6.2 (U) Four

equivalelll bondina elcc1ron
(bl Three bondina
electron
repelled by
a nonbondina pair of
electrons.
..,
I hi
' Ahhoop lhe elcclron pair rcpulsioo r:nki"' hu been widely Ul'ed to "'liunalizc
""""'
lheorttical
suaesa 1hal bondina p:rir-bondina pllir rcpWion is impottalll in k<q>ina 1hcm
..,:vt: lhe tenolcncy for the nonbondirc p:Ws 10 assumes charocler peep 2251 t:1r1 be
rnlher
tlnn lone pair-lone pair repulsion to upluin rcrlucliono in bond oncfes. See Hall, Ill. B. J. Am.
Clu-m. Soc. 19711. 100. 633J.-6llll:
lf78, 17, 226t-2269; Shuslorovich, E.: ll<lbosh.
P. A. J. Am. Clrnn. Soc-. tm . 101. 409G-109S.
-08
6 The Structure and Reactivity af Molecvles
H---------1>-H
ro9r
r .o.,.
11
lbl
1<1
Fig. 6.3 (a) The moluul.ar Slructure of me1hane. (b) The molecular
of ammonia
showina the reduction of bond angles. (c) The molecular structure of wBJer showing the
greater reduction of rhe bond angle by 1wo lone pairs.
As a general rule, we can state that the lone pair will always occupy a ueater
angular volume than bonding elect.rons. Furthermore, if given a choice, lhe lone pair
tends to go to that position in which it can expand most readily . Consider. for
example. the following molecules, where if in each case we consider only the bonding
electrons, we obtain wrong predictions concerning the geometry of the molecules. For
example, BrF3 would be trigonal, IC14 tetrahedral, IF5 trigonal bipyramidal, and SF4
tetrahedral . In fact, none of these molecules has the structure just assigned to it. If,
however, we include the lone pairs, we can predict not only the approximate molecular shape but also distortions which will take place.
Sulfur retrqfluoride (C1.). The molecule :SF4 has ten electrons in the valence shell of sulfur, four bonding pairs and one nonbonding pair. In order to let
each pair of electrons have as much room as possible. the approximate geometry
will be a trigonal bipyramid, as in PF5 However. the lone pair can be arranged in
one of two possible ways, either equatorially (Fig. 6.4a) or axially (Fig. 6.4b). The
experimentally derived structw-e is shown in Fig. 6.4c. The lone pair is in an
equatorial position and tends to repel the bonding pairs and cause them to be bent
back away from the position occupied in an undistorted trigonal bipyramid. We
can rationalize the adoption of the equatorial position by the lone pair by nOling
that in this position it encounters only two 90" interactions (with the axial bonding
pairs), whereas in the alternative structure it would encounter three 90" interac-
(II
(<)
6.4 Sulfur retralluoride. (a) Trigonal bipyramidal slnlcWre wilh t'quatoriallone pair.
(b) Trigonal bipyramidal slnlCture whh tuiallone pair. (c) ExperimentaUy detennined
structure of sulfur teuOI!luoride .
ne Structure of Molecules
209
lions (with the equatorial bonding pairs). Presumably the 120" interactions are
sufficiently relaxed thai they play no important role in detennining the most stable
arrangement. This is consistent with the fact that repulsive forces are important
only at very small distances. In any event, lone peirs always adopt positions
which minimize 90" interactions.
Bromine trifluoride
The :BrF3 molecule also has ten electrons in the
valence shell of the central atom, in this case three bonding pairs and two lone
pairs. Again, the approximate structure is trigonal bipyramidal with the lone pairs
occupying equatorial positions. The
from lone pair repulsion causes the
axial fluorine atoms to be bent away from a linear arrangement so that the
molecule is a slightly "bent T' with bond angles of 86" (Fig. 6.5a).
Dic:hloroiodate(l) anion (Dm1,). The : ICii anion has a linear structure as
might have been supposed naively. However. note that three lone pairs are
presumably still stereochemically active, but by adopting the three equatorial
positions they cause no distortion (Fig. 6.5b). [A note on bookkeeping for ions:
Add 7 electrons (I) + 2 electrons (2CI) + I electron (ionic charge)
10
S pairs.]
Pentajl'uorotetlurate(IV) anion (C4 .). In the :TeF; ion the tellurium atom
has twelve electrons in its valence shell. five bonding pairs and one nonbonding.
The most stable arrangement for six pairs of electrons is the octahedron which we
should expect for a first approximation. Repulsion from the single lone pair should
cause the adjacent fluorine atoms to move upward somewhat (Fig. 6.6a). The
resulting structure is a square pyramid with the tellurium atom 40 pm below the
plane of the four fluorine atoms (Fig. 6.6b).
Tetrac:hloroiodate(lll) anion (D411) . The : IC14 anion i.s isoelectronic with
the TeF; ion with respect to the central atom. In this case, however, there are
four bonding pairs and two lone pairs. In an undistorted octahedron, all six points
are equivalent. and the lone pairs could be adjacent. or cis (Fig. 6.7a); or trans
(Fig 6.7b), opposite to one another. In the cis arrangement the lone pairs will
compete with each other for volume into which to expand, a less desirable
arrangement than trans, in which they can expand at the expense of the bonding
pairs. Since the lone pairs are not seen in a normal structural determination. the
resulting arrangement of atoms is square planar (Fig. 6.7c).
F
Ia)
(b)
F;g. 6.5 (a) The molecular StrUCture of bromine uifluoride. (b) The structure of the
dichloroiodate(l) anion.
210
6 T1le Structure 011d Reactivity of Molecules
(b)
I I
Fig. 6.6 (al The penl3ftuoroleUurale(I V) anion. Awoximlllely oaahcdral arnnaemen1 of

bonclina 3lld nonbondin&
(b)
delermined suuc1ure. The tdurium
atom is brlow 1he plane of the ftoorine lloms. ( From Maslin. S . H.; Ryan, R. R. : Asprey.
L. B. llforx. CJ,n. 1910, 9, 2100-2 103. Reproduced with permission.(
Ia I
(bl
td
F'og. 6.7 The telrnchloroiodulclllll ion. Ia) Octahedral arra11gemen1 of bondif11 and
nonbondif11 electrons wilh lone poin cis 10 each olhe.-. (b) Octahedral orrangemenl of
bondif1131ld nonbondif11 elcclrons wil h lone pairs Irons 10 eoch other. (c)
dele.-mined $1nJCiurc.
NitrtJ/:('11 diaxidl!
11itritl! io11 (C2.,) . utrd nitryl ion
The lhree
N02 No;-. and No;.
lhe effect of sleric repulsion of bonding and
nonbonding cleclrons. T he Lewis strucrures ure
The niuyl ion. No;. is isoelectronic wi1h carbon dioxide and will, like il, adopt a
linear structure with two., bonds (Fi&:. 6.8a). The nitrite ion. NOi'. will have one
7tbond (stereochemically inactive). two ubonds, and one lone pair. The resulling
strucrure is therefore expected 10 be trigonal. with 120" spl bonds to a first
approximation. The lone pair should be ex peeled 10 expand at the expense of the
bonding pairs, however, and the bond anile is found to be 11.5" (fig. 6.8b).
The nilrogen d ioxilk molecule is a free r.ldiCll. i.e., it contains an unpaired
electron. h may be considered to be a nilrite ion from which one electron has been
removed from lhe leas! electronegative atom,
Instead of having a lone
pair on the nitrogen . it has a single electron in an approximately trigonal orbital.
Since a single electron would be expected to repel Jess than two, the bonding
Tbe Structun of Molecul..
Cal
Fog. 6.8
211
eel
Cbl
linem- nitryl ion. N<>;". (b) The effect of the lone pair in the niui te ion. NO! .
Resonance has been omined to simplify the discussion. (c) The effect d the unpnired
(a) The
electron. half of a lone pair, in nitrogen diol<ide.
electrons can move so as to open up the bond angle and reduce the repulsion
between them (Fig. 6.8c).
Phosphorus
(C3.). The imponance of
rrpulsions nl!ar
nuclt!us
Cf!ntra/ atom is nicely shown by the bond angles in phosphorus
trihalide molecules: PF3 ., 97.7", P03 = 100.3", PBr3 = 101.0", Pl 3 = 102". The
immediate inclination to ascibe the opening of the bond angles to van der Waals
repulsions between the halogens must be rejected. AI!Jiou&h the van der Waals
r.Jdji increase F < 0 < Br < I, the
radii and hence the P-X bond
lengths also increase in the same Ofder. The two effects cancel each other (see
Problem 6. 15). The important factor appears to be the ionidty oCthe P-X bond.
The more dectronegative fluorine atom attracts the bonding electron pairs away
from the phosphorus nucleus and allows the lone pair to expand while the
F-P- F angle closes. Reduced bond angles in nonmetal fluorides are commonly
observed. For the small atoms nitrogen and o xygen, where the VSEPR interactions seem to be espec.ially important,
ftuoridl!s havl! smollu bond anglt!S than
tht! hydridt!s (NF3 = 102.3", NH3 107.2", OF1
103. 1", OH 2
104.5").
Gillespie has disctlssed the effect of substiluem electronegativity and pointed out
that the expansion of lone pairs relative to
pairs may be viewed simply as
an example ofthe extreme effect when the nonexistent "substituem" on the lone
pair has no elearonegativily at all (see F'ag. 6.9).
(C2,.) . Fluorine and oxygen utoms ure about the same size
ll!ld similar in electronegativity; therefore we miht expect OCF2 to huve a mther
symmetrical structure. There are no lone puirs on the carbon atom, so to a first
approximation we might expect the molecule to be planar with approximately 120"
<D
-(II
fbi
1<1
Cdl
of X on the size or a bond ina pair of

de<:trons: (a) dedronqaJivity X > A, (b) declronqativily X A, (c) dcc:troncptivity
X < A, (d) X lone pair of dectrons : efreulve electronqarivity ol X is zero. (From
Gillespie. R. J. J .
Edut:. 197t. 41, 18. Reproduced wilh penrrWion.l
Fig. 6.9 Effect of decrcasina
212
6 The Strvcture and Reactivity af Molecules
Fig. 6.10
(a)
Possible
s1ructure ol OCFt.
Asrows indicale smolt
distortions resulting from
and size
(a)
effects. (b) Actual

molecular structure of
OCF2 Note small FCF
bond al18le.
(b)
bond angles (Fig. 6.10a). The molecule is indeed planar but distorted rather
severely from a symmetrical trigonal arrangement (Fig. 6. 10b). It is apparent thai
the oxygen atom requires considerably more room than the fluorine atoms. There
are at least two steric reasons for this. First, the oxygen atom is doubly bonded to
the carbon and the C=O bond length (120 pm) is somewhat less than that d
C- F (135 pm); thus, the van der Waals repulsion of the oxygen atom will be
greater. More important in the present case is the fact that the double bond
contains two pairs of electrons, and whether viewed as a <T-'IT pair or twin benl
bonds. it is reasonable to assume that they will require more space than a single
bonding pair.
This assumption is strengthened by other compounds with double bonds. In
the OSF4 molecule the doubly bonded oxygen atom seeks the more spacious
equatorial position, and the fluorine atoms are bent away somewhat from the
other two equatorial and the two axial positions (Fig. 6.1lb). Further examples
are listed in Table 6.1. Note that the behavior of the doubly bonded oxygen atom
is in several ways similar to that of a lone pair. Both require more room than a
single bonding pair, both seek the equatorial poSition, and both repel adjacent
bonds, thereby distorting the structure. For example, compare the structure of
OSF4 (Fig. 6.1lb) with that for SF4 (Fig. 6.1 Ia). However, Christe and Oberhammer4 cite one major difference: The lone pair in SF4 is cylindrically symmetrical
whereas the 7f bond in O=SF4 will have greater electron density in one plane
OJ/
s,
I
f..F
' c= s1.-
/
I'F
A>ial FSF anc1<

(idclliz.ed s 180")
179"
EquMoriol FSF .,.;le

ridoaliud ; I :ZOOI
103'
110*
97"
11
(b)
(C)
178.S'
170"
Fig. 6.11 Molecular structures of (a) sulfur Jetl'1llluoride; (b) thionyl Jctrnftuoride;
(c) methylene sulfur letraftuoride; the hydrosen atoms are in a vertical pCane wilh the axial
fluorine a1oms.
Cbrisle. K. 0.; Qberlwnmer. H.lnorg. Chrm. 1981.20.296. Ncte lhat lhe bond angles accepted by
Cbriste and Oberhammer were somewhat clilferent than those given here and were somewhai man J
favorable for their
araumenr.
T\e SlrVcture of Molecules
213
, ...... 6.1
Molecule
X-Y-x<'
108"
9t/'
103.3"
110,178.5"
Molecule
X-Y-x<'
:GeF2
:SF2
94" :t f'
98"
:SF4
103.179"
82,89"
:IF,
0;-0:,.
"! - Central atom, C, S, P, I, Ge; X
I(
J:J. ;,
..\.
roo.:s-
:PO,
82"
haloacn a&om.
"" -
!han another. However, the plane of the .,. bond can only be inferred from the
bond angles, leading to a possible circularity in reasoning. More straightforward is
the CH2 SF4 lllQiecule (Fig. 6. l lc). Because the hydrogen atoms lie in the CSF2
axial plane; we know that the .,. bond involving a p orbital on the carbon atom
must lie in the eqUJJtoria/ plane of the molecule . And the resulting repulsion
between the .,. electrons and the electron pairs bonding the equatorial fluorine
atoms is dramatic: The F,q-Fq qle has been reduced to 97".'
No discussion of the VSEPR model of moleculnr structure would be complete

without a brief diSCllssion of some problems remaining. One interesting problem is the
molecular structure of XeF 6 The simpl.e st MO treatment of this molecule predicted
that the molecule would be perfectly octahedral.6 In contrast , the VSEPR model
considers the fact that there will be seven pairs of electrons in the valence shell (six
bonding pairs and one lone pair) and predicts a structure based on seven-coordination.7 Unfortunately, we have little to guide us in ohoosing the preferred arrangement.
Gillespie suggested three possibilities for XeF6 : a distorted pentagonal bipyramid, a
distorted octahedron. or a distorted trigonal prism. The lone pair should occupy a
definite geometric position and a volume as great as or greater !han a bonding pair.
Unfortunately, only three neutral fluoride molecules with seven bonding pairs are
known: IF7, ReF7, and OsF7. The structures are known with varying degrees of
certainty, but all three appear to have approximate DS/t symmetry, a distorted pentagonal bipyramid (Fig. 6. 12).8 Unfortunately, knowing the MF7 structures was of
Fig. 6.12 MolecUlar
structure of iodine
he.ptaftuoride.
' Huheey, J . E. Inorr.
a.,m. t981, 20, 4033.
A disaJssiono(molecularorbilal lhcory applied 10 noblcp.s CCC'I1!>0Unds will be found inehapler t7.

1 Gillespie. R. J. In Noblr Gas O>mpO<UKis; Hrman. H. H., Ed.; UnM:tsily o( Chita&o; Ctiaao.
1963; piD.
I
Drew, M. G. B. Prorr. ltrorr. Otmr. lf77, ZJ, 67.
214
6 The Structure and Reactivity of Molecules
little help in sludying XeFt, because the pentagonal bipyramidal slruc(Ure was the first
lo be experimenmlly eliminated as a possibility. A number of other flu oro complexes
with coordination number 7 are known: [ZrF,f- . known in both pentagonal bi
pyramidal and capped trigonal prismatic fonns: the [NbF7 12 - anion is a capped
octahedron."
Determining the exuct structure of the gaseous XeFb molecule proved to be
unexpectedly difficult It is known to be a slightly distorted octahedron. In contrast to
the molecules discussed previously, however, tlte lone pair appears to occupy less
spte tlwn the bending pairs. The best model for the molecule (Fig. 6. 13) appears to
be a distorted octahedron in which the tone pair extends either through a face (C3
symmelry) or through an edge (C2 , . symmetry).ao.u
The conformation of lowest energy appears to be that of C3 symmetry. Part of the
experimental difficulties stems from the fact that the molecule is highly dynamic and
probably passes through several conformations. In eilher of the two models shown in
Fig. 6.13, the Xe- F bonds near the lone pair appear 10 be somewhat lengthened and
distorted away from the lone pair: however. the distortion is less than would
been expeded on the basis of the VSEPR model. That the latter model correctly
predicted a distortion at all at a time when others were predicting a highly symmetrical
and UF6 are pcrfeclly ococtahedral molecule (all other hexafluoride such as
tahedral) is a signal success. however.
The powerful technique of X-ray diffraction cannot be applied to the resolUiion of
this question since solid Xeft. polymerizes with a completely different structure (see
below). However. the isoelectronic compound Xe(OTeF,)h crystallizes as a simple
molecular solid. so that it muy be studied by X-ray diffraction . Each molecule has
symmetry (for the oxygen coordination shell about the xenon) indicating a stereochemically active lone pair (Fig. 6.13a). suggesting the same struclUre in XeF., as
well. II
Even more puzzling are the structures of anions isoelectronic with XeF6 Raman
spectroscopy indicates that the tF; anion. like XeF.,. has lower symmetry than
c,,.
tbt
Fig. 6.13 Possible mok:cubr structures of xenon hexafluoride: Ia) Ione pair emerging through
face of the oc:t:lhcdron. C,, symmetry: (b) lone pcir emerging shrol!ih edge of octahedron.
Cl symmetry. [From Gavin. R. M.. Jr.: 1!:111ell. L. S. J .
PI. t968. 48. 24M.
Reproduced with pennission.l
the numher or d electrons in u complex can nlfcc1 its st:lbility ond gcomesry
(Chnplcn II nnd 121. The examples given here were chuscn to have ad" conlit;urn!ion.
Y We sht>ll see 1hu1
"'Cavin. R. M . Jr.; Barten. L. S. J. Clwm. Phy. 1968. 48. 2466.

" Sewell, K.; l..cnlz. 0. Pmxr. /nnq:.
198Z.. 19. IT.!-11!0.
The Stnlcture of Molecules
21 S
octahedral. but !.h at BrF,7 is octahedral on the spectroscopic time

Both are
fluxional on the NMR time scale.J Anions such as Sbx:,-.
(X =Ct. Br. or ll.
and BrF;: have been assigned perfectly octahedral structures on the basis of X-ray
crystallography. 14 For lhcse structures in which the lone pair is stere.ochemically
inactive, it is thought that the pair resides in an s orbital. This could result from seric
crowding of the ligands or the s1ability of the lower energy s orbital, both. Raman
and infrared spectroscopy have indicated. however. !hat rhese ions may be either
non octahedral or extremely susceptible to deformation. u
Complexes of usenic(ll ll. anrimonytlll). [elecron configuration
111 - I)
diOnsll,lead(ll), and bismUih(lll) ((n - 2lf14 (11 - I)Juns2} with polydentate ligands
occupying six
sites have been fouoo to have a stercochemically acrive
lone pair. However. the dichotomy of behavior of the heavier elemen1s that have a
lone pair is reflected in I he crystal chemisry of Bi1 .. . When forced into sites of high
symmetry. the Bi3 + ion responds by assuming a spherical shape; in crystals of lower
symmetry I he lone pair asserts itself and becomes stereochemically active.t
There appears to be no simple .. besl'' interpretation of the stereochemisrry of
species with 14 valence electrons. Rather. it should be noted that there seem to be
several structures of comJl'}rable stability and small forces may tip rhe balance in favor
of one or the other. An example of the balance of these
is the trans isomer of
tetrachlorobis(tetramerhylthiourea)tellurium( IV) which provides a very interesring
story. This compound was synrhesized and seJl'}rated as orthorhombic crystals which
contained cenrrosymme1ric molecules consisting of approximately octahedral arrangements or four
and two sulfur atoms about each tellurium atom. However.
when the:se crystals were examined several years later. it was found thllt most had
changed to a monoclinic form. When the X -my structure was determined. it was found
that the monoclinic
contained severely distorted molecules (Fig. 6. 14a) with
roost angles decreased to aboUI 80". but one opened to 106" (compared to approximately 91\1' in the orthorht)mbic form).J7 Apparently the orthorhombic
mt)Jecules in which 1he lone pair has been foroed into a stereochemically inert s orllital
(as is
while the monoclinic form has a stereochemically active lone pair
presumably protruding within the 106" bond angle (Fig. 6. 14bl. Consistem with this
interpretation is the lengtheniflG of 1he Te-S and Te-CI oonds a<ljacen to the lone
pair. Such lengthening is commonly found and may be interpretell in terms of the increased LP-BP repulsions. It is tempting to suggest that crystul symmetry forces the
lone pair to be sJercochemically inac1ive in the orthorhombic form and that the prolrusion of the lone pair
the crystal :symmetry to change. However. 1his tends to
oversimplify what must be a llclicate
of crystal Jl'}Cking forces and electronic
effects .
., Cllri'<tc. K. 0 .; Wiloon. W. W. hmr11. Clk'm. t9119. 18. 3276-3277.

o) The lime scale o{ speclroscopic ond olhcr lcchniqucs is
in T:lblc 6.S. and fluxional or
rnolub ore discUAA<d on PI' !31-243 und in Cbutltcr IS.
,. l..awlon. S. L.: Jacobson. R. A. /nm11. Clrmo. 1966. 5 . 743. M;JtUoub. A. R .; Haser. A. ; Fucho. J. ;
Scppcll, K. JIII.(C'W. Ch<m. Int. Ed. Enxl. 19119. 18. IS26-IS27.
15
Adams. C . J.: Downs. A. J. Chtm. C<Hnmwn. t910. 1699.
"'Shannon. R. D. Jlc"ko Crystallu11r. !916. AJ2. 1St. Kcpert. D. L PrtJIIr. lnnr11. Chtm. 1911. 2J. 1.
See ol50 Allricl. w. Jlta Cr;v.rta&tr. Sc:t. 8 t9116. 842. 449.
o7 fupc:rA.<. S.;
J . W. : Huscbye, S. : Miblsen. 0. Aria. Ch,m. ScunJ. Sect. Jl 1915. 29.
141-148.
216
6 The Structure and R-ctivity o l Molecules
(1>1
Fig. 6..14 (a) Molecular slru= of

in
the monoclinic form. Note that the line CI(4)- Te-CI(2)
an ax.is for a
pcn123onat bipyramid if it is assumed thai a lone pair occupies a pc>sOtion between S(t) and
Cl(J) (b). (In p;u:t from E5pcrh, S. ; George., J. W. ; Husebye, S. ; Mikalsen. 0. Acta CMm.
Scand. 1975.19A, t4t-148.)
Finally, it should be noted that the XeF6 molecule exhibits a definite tendency to
donate a fluoride ion and form the XeF; calion, which is isoelectronic and isostructural with IF5 as expected from the VSEPR model. The structure of solid XeF6 is
complcx. 18 with 144 molecules of XeF6 per unit cell; however thete are no discrete
XeF6 molecules. The simplest way to view the solid is as pyramidal XeF; cations
exten.,ively bridged by "free" fluoride ions. Obviously, these bridges must contain
considerably covalent character. They cause the xenon-containing fragments to duster into terrahedral and octahedral units (Fig. 6.1Sa,b). There are 24 tetrahedra and
eight <!ttahedra per unit cell, packed very efficiently as pseudospheres into a Cu1 Au
structure
6.15c).II.19The structure thus pi'Ovides us with no information about
molecular XeF6 , but it does reinforce the idea that the VSEPR-correct, square
pyramidal : XeF$ is structurally stable.
II Then:
are actualy four phases known o( aclld xenon heuf!IJC)(ide. AI t.'I'C seven! uructunl
in common, and the phase described here, phasc IV or the cutJic pbue. is the eaJiest 10
19 Burbank. R. 0 .; Jones, G. R. J . Am.
CMm. Soc. 19"14, 96, 4)-4,
The Strvcture of Molecules
( a)
(b)
217
lei
Fig. 6.15 The srrucwn: of solid XeF6 Each Xe arom sits at the base of a square pynmid of
five fluorine atoms. The bridging fluorine aroms an: shown as larger circles. (a) The
tctramcric unit with the Xe atoms forming a tetrahedron, (b) the hexameric: unit wllh the Xe
atoms fonning an octahedron. {c) the Cu,Au structure: The shaded circles represent the
octahedral clusters and the open circles the tetrahedral clusters. (In pan from Burt>anlc R. D.;
Iones, G. R. J . Am. Ch<tm. Soc. 1974, 96, 43-48. Used with permission.(
Another problem arises with alkaline halide molecules, MX1 . These molecules
exist only in the gas phase-the solids are ionic lattices (cf. CaF2, Fig. 4.3). Mosl MX2
molecules are linear, but some, such as SrF2 and BaF2 , are bent.tO If it is argued that
the bonding in these molecules is principally ionic and therefore not covered by the
VSEPR model. the problem remains. Electrostatic repulsion of the negative anions
should also favor a 180" bond angle. At present. there is no simple explanation of these
difficulties, but the phenomenon has been treated by means of Walsh diagrams (see
page 218).
Summary of
V SEPR Rules
The preceding can be surn.med up in a few rules:

I. Electron pairs tend to minimize repulsions. Ideal geometries are:
a. for two electron pairs, linear.
b. for three electron pairs, trigonal.
c. for four electron pairs. tetrahedral.
d. for five electron pairs, trigonal bipyramidal.
e . for six electron pairs, octahedral.
2. Repulsions are of the order LP- LP > LP- BP > BP-BP.
a. When lone pairs are present, the bond angles are smaller than predicted by
rule I.
b. Lone pairs choose the largest site, e.g., equatorial in trigonal bipyramid.
c. If all sites are equal, lone pairs wiU be trans to each other.
3. Double bonds occupy more space than single bonds.
4. Bonding pairs to electronegative substituents occupy less space than those to
more electropositive substiluents.
>D
Bilchler, A. ; Stauffer, J. L.; Klernperer. W. J . Am. C/r<tm. Soc. 1964.86, 4S44-4S50. Calder. V.;
Mlllm, D. E .; SeWdri, K. S.;
M.; White, D.J. Chem. Phys. 1969,51, 209}-2099.
218
6 The Stl'ucture and Readivity of Molecules
To the above Drago2t suggested the following empirical rule which rationalizes the
very small angles (-90") in phosphine, arsine. hydrogen sulfide, etc., and which is
compatible with the energetics of hydridiurion (page 22S):
S. If the central atom is in the third row oc- below in the periodic table. the lone
pair will occupy a stereochemically inactives orbital and the bonding will be
through p orbitals and near 90" bond angles if the substituent electronegativity
iss -2.S.
Because of its intuitive appeal and its high degree of accuracy, the VSEPR model
has been well received by inorganic chemists. but the theoretical basis has been a
mauer of some dispute.n Moc-e recently. there have been strong theoretical arguments
for localized. stereochemically active orbitals.n
Molecular Orbitals
and Molecular
Strudure
Because VB methods deal with easily visualized, localized orbilals, stereochemical

arguments (such as the VSEPR model) have tended to be couched in VO terminology.
Several workers24 have attempted to modify simple LCAO-MO methods to improve
their predictive power with respect to geometry. The basis for these methods consists
of Walsh diagrams23 that correlate changes in the energies of molecular orbitals
belween a reference geometry, usually of. high symmetry, and a deformed structure of
lower symmetry. Consider the BeH2 molecule discussed previously. In the preceding
discussion only the filled. bonding orbitals were emphasized although Olher types of
orbitals were mentioned. Figure 6.16 illustrates what happens to the energies of all the
orbitals in BeH2-bonding. nonbonding, and antibonding-as the molecule is bent.
Consider first the 2cr, orbital. It is constructed from atomic wave functions that ure
everywhere positive, and hence on bending there is an increase in overlap since the
two hydrogen wave functions wiU overlap to a
greater extent (recall that the
wave function of an aaom never goes completely to zero despite our diagrammatic
representaaion as a finite circle). The energy of the 2u., orbital (relabeled 2at) is
lowered somewhat. In contrast. the energy of the Ia;, orbital increases on bending.
This is because the wave function changes sign (as shown by the shading), and overlap
of the terminal hydrogen wave functions will be negative. In addition. lhe overlap of
the hydrogen atoms with the linear p orbital must be poorer in lhe be.nt molecule, and
so lhe energy of the lu, orbital (relabeled
will increase more than 2iz 1 will
decrease. BeH2 has a molecular orbital electron configuration 2 1 .or 2ui 1 and
since lb2 1oses more energy than 2at gains, BeH2 is linear. not bent.
Similar arguments can be applied to the nonbonding and anti bonding orbitals (Fig.
6.16: see Problem 6.7). In the water molecule.
with eighl valence electrons, the
u; u;.
" llrago. R. S. J.
Educ. 1973. j(), 244-24S.

u Edmiston. C. ; Banteson. J.: Jarvie. J . J. Jim. Ch<-m. Soc. 1986. 108. 3S93-3S%; Ptllke, W. E.;
Kirtmen. B. J . Jim. Clwm. Soc. 1978. /1)(). S717-ffil. See also Footnote 3.
:>Bader. R. F. W.; Gillespie. R. J. : MACDougall. P. J. J. Jim. Clwm. S. 1911. 110. 7329-7336: In
Fmm JltomstoPulymn.: /st)<'wctronic
Liebman.J . F .: Cn:cnberg, A .. Eds: VCH: New
Vorl<. 1939: pp l-SI. Bader. R. F. W. Jltomsln Moluults: Oxford Univusily: Oxford. 1990.
Bartc:ll. L S.; Barshacl. Y. Z. J. Am.
S. 1984, 106. no<>-1103.
"See. for example. Cim:tre. 8 . M. Jlcc. Chtm. Ru. 1974, 7. 384-392;

Bending: Academic: New Yori<. 1980. and FO<llnotc 2S.
n Walsh. A. D. J . Cl,m, Sex:. 1953. 2260-2331.
Strttctuu anti
T\e Strudure of Molecules
219
Fig. 6.16 Molecular orbilal

pictures and qualilalive
ene,.;es of linear and bent
AH2 molecules. Open and
wiled areas represe.n t
bml
dilfetenc:es in sian ( + or
- ) or I he wave functions.
Changes in shape which
increase in-phase overlap
lower Jhe molecular orbital

enerJY. [From Gimarc.
Jo.
I
;
. I
\
I
I
'-"'
??!
__
.....
Ju,
B. M. J . Am.
Soc.
1971. 93, 593. Reproduced
with pc:rmission.J
220
6 The Structure and Reoc:tivity of Molecules
MO configuration will be za; lo-! lw}.,.l.,.!,. (or

Because the formerly nonbonding 1.,.,_.. orbital is grearly stabilized (3a 1) on bending, the water molecule is bent rather than linear.
The Walsh diagr.1m shown in
6.16 is accurate only for molecules in which
there is a large separation between the ns and np energy levels of the central atom. If
the ns-np separation is small (as in SrF2 and BaF2). the lb2 level (of Fig. 6.16) does
not rise as rapidly as 2a 1 falls, and the molecule may be stabilized on bending.26 Note
that in MF2 molecules of this type. the 3a 1 and lb 1 levels are unoccupied.
This brief discussion cannot do justice to the MO approach to stereochemistry.
but it does illustrate the reduced importance of electron-electron repulsions (usually
omitted in simple approximations) and the increased importance of overlap in this
approach. Although the VSEPR approach and the LCAO- MO approach to stereochemistry appear on the surface to be very different. all valid theories of bonding,
when carried sufficiently far, are in agreement that the most stable molecule will have
the best compromise of (I) maximizing electron-nucleus attractions and (2) minimizing electron-electron repulsions.
Strudure and
Hybridization
As we have seen in Chapter s. it is not correct to say that a particular structure is

..caused.. by a particular hybridiz.ation, though such factors as overlap and energy are
related to hybridization. We have also seen the usefulness of viewing structures in
terms of VSEPR . We shall encounter yet further factors later in this chapter. Nevertheless it is appropriate and useful to note here that certain structures and hybridizations are associated with each ()(her. Some Of the most common geometries and their
corresponding hybridizations are shown in Fig. 6.17. In addition. there are many
hybridizations possible for higher coordination numbers, but they are less frequently
encountered and will be introduced as needed in later discussions.
The possible structures may be classified in terms of the coordination number of
the central atom and the symmetry of the resulting molecule (Fig. 6.17). Two groups
about a central atom will form angular (p2 orbitals,
symmetry) or linear (sp hybrid,
D.,h symmetry) molecules; three will form pyramidal (pl. C1.) or trigonal planar (spz,
Dlh) molecules; four will usually form tetrahedral {spl, Td) or square planar (Jsp2.
D4h); five usually form a trigonal bipyramidal (Dlh) more rarely a square pyramidal
(C4 .) molecule (both Jspl hybrids. but using different orbitals, see Table 6.2): and six
groups will usually form an octahedral molecule (d2spl, Oh).
If in addition to the bonding pairs there are stereochemically active lone pairs. the
symmetry will be lowered (BF1 is Dlh; NF1 is C1.). Furthermore. the hybridization of
the lone pair{s) will be different from that of the bonding pairs (see below).
Most hybridizations result in equivalent hybrid orbitals, i.e., all the hybrid orbitals are identical in composition <% s and %p character) and in spatial orientation
with respect to each other. They have very high symmetries, culminating in
letrahedral and octahedral symmetry. In the case of Jspl hybrid orbitals. the resulting
26 See Burdett. J. K. Moluttlar Shopts; Wiley: New Yen, 1980; Chaplef'4; Albriahl. T. A.; Burdett,
J. K.; Whangbo, M. H.
in Ciwmillry; Wiley: New Vorl(. 1985; O>aplcr7.
Structure and Hyhridization
p'
o"'..
c,.
c,.
Fig. 6.17 Geometries of some common h)brid alld nonhybrid bonding arrangemems. S
lines represent bonds formed from the oroitals on the centralutom @. The dashed lines
geometric lines added for perspective.
Table 6.2
Compon.m olamic arbitols

Involved in hybrid orbital
fonnotian
Atomic ort.itals
sp, spl, sp3

dsp2
dsp' (TBP)
dsp' CSP}
tfZspl :!
222
6ne Structure and Reacrivity af Molecules
orbilll!s are IIDt

We shall see that the trigonal bipyramidal hybridization
results in three strong equatorial bonds (spl lrigonal orbitals) and Jwo weaker axial
bonds (dp linear orbitals). The square pyramidal hybridization is approximately a
square planar Jspl set plus the P: orbital. As in the trigonal bipyramidal hybridization.
the bond lengths and strengths are different.
The relation between hybridization and bond angle is simple for s-p hybrids. For
two o r more equivalent orbitals, the percents character (S) or percent p character (P)
is given by the relationship;27
S
P - 1
cos8=--= - -
S- 1
(6.1)
where 8 is the angle between the equivalent orbitals (") and the s and p characters are
expressed as decimal fractions. In methane. for example,
0 25
cos 8 = -0.7.5
= -0. 333 ;
8 .. 109S
(6.2)
In hybridizations
noneqtJivalent hybrid orbitals, such as sp'icl. it is
usually possible to resolve the set of hybrid orbitals into subsetS of orbitals that are
eqtJivalent within the subset , as the spl subset and the Jp subset. We have seen
(Chapter .5) that the nonequivale.nt hybrids may contain frac!ional sand p character,
e.g., the water molecule which uses
orbitals midway between pure p and spJ
hybrids. For molecules such as this, we can divide the four orbitals imo the bonding
subset (the bond angle is 104!") and the nonbonding subset (angle unknown). We can
then apply Eq. 6.1 to each subset of equivalent orbitals. In water. for example, the
bond angle is 104i". so
P - 1
cos 8 = -0.2.50 = - pp = 0.80
80"/. p
character and 200/. s chnracter
(6.3)
(6.4)
Now of course the total p character summed over all four orbitdls on oxygen must be
Px + Py + p,) and the totals character must be 1.00. If the bonding orbitals
contain propor1ionately mou p character, then the nonbonding orbitals (the two ton..
pairs) must conmin proportionutely less p character, 70%: (0.80 + 0.80 + 0.70 +
0.70 = 3.00 (p); 0.20 + 0.20 + 0.30 + 0.30 1.00 (s)). The opening or some bond
angles and closing or others in nominally "tetrahedral" molecules is a common
phenomenon. Usually the distonion is only a few degrees. but it should remind us that
the terms "trigonal," " tetrahedral." etc. usually are only approximations. Exactly
trigonal and tetrahedral hybridizations are probably restricted to molecules such as
B01 and CH 4, in which aU the subst.ituents on the central atom are identical. We see
3.00 (=
n Equalion 6. 1 is rairicled 10 molecde.s such as w:11er in whidlthe anale iJ known bclween two
e<J>ivalcnl ortilals
. the two Glbilals bindirc the hydrocen .....,.,. Equivalent and nonequivalent h)'llridsarediscvssed further on piCC 227. Sec Direct. W. A.; Luuke. W. -'111""' Clwm.
19111,10. 899-911: Baisen.. M. B. Jr.: Gibbs, C.. V . l'lrys. Cltrm.. Mlnnols ll'l7,/4, Jn..J76; Grim.
S. 0 .: Plastas, H. J.: Huheey, C. L : Huheey.J. E. I'Msplro,.,lf71,1,
Sec also McWeeny.
R. CO<bon's Vokn; Odord Universliy: Oxlorcl. 1979; pp 19S-t9!1. The
of!M method
has been queslione4: Maarusson. E. J. Am. Clwm. Soc. 1914. tOIS. t117- lt&5. t t&S-It9t. The lack
or aarecment revolves around the queJiion of the onlqonality ct hybrid ort>ilak.
Struchwe and Hyl>ridixotion
223
this distortion epitomized in AL5 molecules. Unlike coordination number's. 2, ), 4,21

and 6. !here is no unique, highly symmetrical set of equivalent orbitals llw can be
constructed for live-coordination. Of the two hybridizations shown in Fig. 6-17, most
compounds of nonmetals favor the trigonal bipyramidal (TBP) structure.29 Many
coordination compounds are known, however. with square pyramidal (SP) suuctures
(see Chapter 12). More important for the present discussion. however. is the fact that
there are many compounds that cannot be classified readily into TBP or SP geometries. Muetterties and GuggenbergerlO have shown that there is a continuous specuum
of compounds ranging from TBP to SP.
(6.5)
TBP
D,.
SP
c..
A list of compounds showing the gradual change from trigonal bipyramidal to

square pyramidal geometry is given in Table 6.3 (see F'18- 6 -18). The gradual change
can be quantified in terms of the dihedral angles between the faces of the polyhedra.
For example, in the conversions shown above, when TBP- SP. the dihedral angle of
the edge furthest from the viewer opens up gradually until it reaches 180", i.e _, the
back face of the square pyramid becomes a plane. The angles of the edges (two of
which are labeled e 1 and e2 in the ligures accompanying the table) are opened up (76").
approaching right angles in lhe pyramid. Now as the reverse change takes place. SPTBP, edge e1 reappears as n "real" edge and et e2 , and e3 all close unlillhey reach
identical values in the idealized trigonal bipyramid. The gradual change in these angles
as one progresses through the list of compounds in Table 6.3 indicates that just about
every possible intermediate between the two limiting geometries is known. When the
various substituents are different (and occasionally even when they are not-see
Chapter 12), these intermediate structures are the rule rather than the exception, and
they should warn us to avoid overgeneralizing a structure to make it fit a preconceived
pigeonhole. As Mueuerties and GuggenbergerJO have said. describing a molecule as
"a distorted trigonal bipyramid" conveys little information as to the extenl of the
distortion and the shape of the molecule_ Methods are available for calculating lhe
location of an intermediate on the TBP-SP spectrum. using the dihedral angles shown
211 Tht
4 c::111 be
cxc:cplion of two stable Slructurcs, of TJ and D., symme&ry. forcoordina&ion number

Tht $<!"""' plarulr Slructurc is known only where there nrc special stabilizif\8
enc.-gics resuflil\8 (rom the J elcelron confi1uration in transition metal compounds.

:to Three ec:qllions arc pclll>l)hcn)lanlimony, pcnta<:yckJt>ropylonlimony, and a bieydic phospbor-
ane ($U Problem 6.16). Howurd. J. A. ; Russell, D. R.; TrippeU, S.
Commrm_1973, 856-857.
and references !herein.
,. Mueuenies. E. L: GusgenbuJcr. L J_ J_ Am. Cltmr. Soc- W74, 96, 1748-1756.
)4
'1ble 6.3
ocleal and observed anga.
'wg) in ML5 complexes
Ideal trigonal bipyramid
63.1, .53.1
.53.1 --+
.53.8, .53.8
.53.8
.54.2, .57.3
.50.8
Sl.8 .52.3
4.5.7
.54..5, .58..5
37.8
Ni(CNI,(il.1, 68.6
32.2
Nb(NC5 H1o),(Nb2)
65.4, 67.0
23.2
Nb(N<;H 1o),(Nbl)
68:6, 70.6
15.8
70.2, 70.2
15.6
(C6 H.s)s8b
68..5, 69.2
14.4
7.5.0, 79.4
0.3
__
__i_d____
7.s_.7_._7_s_.,_____o_
.o_-__
Muetlerties, E. L; GugcnberJer, L J . J. Am. Cltem.
Soc. 1974, 96, t748-t756.
These two structures occur in lhe unit c:dl of the
salt.
A--4--+
NtxNC,H 10 ),
Sb(C.Hsls
Ni!CN,;-
fig. 6.18 Real live-coordinate molecular structures illustr.uing i ntermediates between TBP
(D...,) on top left 10 SP (C.,.) on the bonom riaht Note Jhaltwo differenl
polyhedra
are found in the unit ceU of the
salt. (From Mueuerties E. L.: Gussenbercer. L. J.
J. Am.
Soc. 1974, 96. 1748. Used with permission.)
in Table 6.3. One can thus quantify the extent of distortion from either ideal structure
toward the other. Thus, by using the dihedral angles in a particular five-coordinate
complex of zinc, it is possible to describe the intermediate structure as 60"/. TBP and
40"/. SP.31
The calculation or sand p character is more difficult if either J orbitals participate
in the hybridization or if none of the orbitals is equivalent to another to form a subset.
lo Sheldrick, W. S.; Schomb<q, D.; Schnclpeler. A. AcUJ Crysrallbgr., Slcr. B 1980. J6. 2316-2323.
Kerr, M. C.; Pralon, H. S.; Ammon, H. L.; Huheey, J. E.; Stewart. J . M. J. Coord.'Ch-. 19111,
II. 111- IIS.
Structure and Hylwidizotion
225
fig. 6.19
properties or hybrid ornitals

from s. p. and d alomic
ornitals. [From Kasha. M.;
adaplcd from Kimball. G.
Ann .
Phys. Chrm.
1951, 1, 1n. Reproduced
with pcrmiuioo.)
-Pc:n:cnt p - ottlit.aCC'h..at'adt:r
In the case of d orbitals, the relation be1ween hybridization and bond angles is given in
Fig. 6. 19 , although the aCC'IIracy is somewhat less than can be obtained from computation. For completely nonequivalem hybrid orbital s, simultaneous equations involving
aU of the bond angles and hybridizations may be solved.27
Bent's Rule and

the Energe tics
of Hybridization
When a set of hybrid orbitals is constructed by a linear combination of atomic orbitals.

the energy of the resulting hybrids is a weighted average of the energies of the
participating atomic orbitals. For example, when cllrbon forms four covalenl bonds,
although there is a promotion energy from ls22s22pl - lsl2s1Zpl. !his is independem
of the hybridization lo the valence state;32
2p=t=E=
2p=p:E
2s---t!-
2s ----lf 1-
n The lc\<d5 sbown are one-dec1ron levels and do not show correlation efl'tcls. See discnuion or the
ener)dics of the valcncc Slale. Chapler S.
226
6 The Strvctu and Reactivity of Molecules
In the phosphorus atom Jhece is liule initial pr-omotion energy: The ground stale is
trivalent, as is the valence state. Note that any hybridization will cost energy as a filled
3s Ofbital is raised in energy and half-filled Jp orbitals are lowered in energy:
3p=p=E
(6.7)
3s-flThis energy of hybridization is of the order of magnitude of bond energies and can
thus be important in determining the structure of molecules. It is responsible for the
tendency of some lone pairs to occupy spherical, nonstereochemiCIIlly actives orbitals
rather than stereochemically active hybrid orbitals (see page 215). For example, the
hydrides of the Group VA (IS) and VIA ( 16) elements are found to have bond angles
considerably reduced as one progresses from the first element in each group to those
that follow (Table 6.4). An energy factor that favors reduction in bond angle in these
compounds is the hybridization discussed above. It costs about 600 kJ mol- to
hybridize the central phosphorus atom. From the standpoint of this energy faaor
alone, the most stable arrangement would be utilizing pure p orbitals in bonding and
letting the lone pair ..sink.. into a pure s orbital. Opposing this tendency is the
repulsion of electrons. both bonding and nonbonding (VSEPR). This favors an ap
proximately tetrahedral arrangement . In the case of the elements Nand 0 the sreric
effects are most pronounced because of the small size of atoms of these elements. In
the larger atoms. such as those ofP. As. Sb. S. Se. and Te. these effects are somewhat
relaxed. allowing the reduced hybridization energy of more p character in the bonding
orbitals to come into play.
Another factor which affects the most stable anangement of the atom in a
molecule is the variation of bond energy with hybridization. The directed lobes of s-p
hybrid orbitals overlap more effectively than the undirected s orbitals, the two-lobed p
orbitals. or the diffuse d orbitals. The increased overlap results in stronger bonds
Bon! angles in the hydrides

of Groups VA (15) a nd
VIA (1 6)o
Structure and Hybricli:o:atian
227
(Chapter .5). The molecule is thus forced to choosen between higher promotion
energies and better overlap for an .r-richU hybrid. or lower promotion energies and
poorer overlap for an s-poor hybrid.
Good examples of Ihe effect of the diffe.r ences in hybrid bond strengths are shown
by the bond lengths in MXn molecules with both equatorial and axial wbs lituents.U
PF5
PCI5
Sb05
sF.
OF3
BrF3
r,q (pm)
r,.., (pm)
1.53.4
202
231
1.54
159.8
172.1
214
243
164
169.8
181.0
JS7.7
An splJ hybrid orbital set may be considered to be a combination of PA? hybrids

and sp,Py hybrids. The former make two linear hybrid orbitals bonding axially and the
Iauer form the trigonal, equatorial bonds. The spl hybrid orbitals are capable of
forming stronger bonds, and they are shoner than the weaker axial bonds. When the
electronegativities of the substituents on the phosphorus atom differ. as in the mixed
chlorofluorides, POxf5 _,, and the alkylphosphorus fluorides, R..,PF5 _ _., it is experimentally observed that the more electrOnCgativc substituent occupies the axial position and the less electroneptive substituent is equatorially situated. This is an
example of Brnt's rnlr,ll> which states: Morr rltctrorztgativt substituents "prefer"
lrybrid orbitals having less s churacttr. unJ man tltcrropositive substitrrents "prefer" llybriJ orbitals having f7W't s charat:rtr. Although proposed as an empirical rule,
in the chlorolluorides of phosphorus, it is substantiated by molecular orbital
calculations.
A second example of Bent's rule is provided by the fluoromelhanes. In CH,f, the
F-C-F bond angle is less lhun 1094", indicating less than 25% s character. but the
H- C- H bond angle is larger
the C-H bond has
character. The bond
angles in the other ftuoromelhanes yield similur resulls (Problem 6.6).
The tendency of more eleclronegalive subslituents to seek out the low electronegalivity p,d<: apical orbital in TBP structures Is often termed "apicophilicily." It
is well illustraleU in a series of oxysulfllranes of the type
O-R
R, l
s:
"
I
R O-R
n T1le molecule. or course. does 1101 " dloosc." bur in o.,.,_ 10 I.Wldcrslllnd i10 bcha>ior. the rlwmur
ITIUSI choose the rdaUYC impcr1ancc.
,. Since moSI otbilal nnae &om0'/.10 SO'/.s th3nietcr. s-ridl Ofbilols 11te those wilh more rhan 2S"/.
chataacr, and s-poor ote those with less than 2S"-'.
JJ
Dola from Wels. A. F. Slructwollll<l'tonic Clttmi.lrry. Slh cd.: Oxford Uni\'aS&y: Oxford. 198-4.
JO
Bent, H. A. J . Clwm. Edur:. 1960, P. 616-62A: Clwm. /WI!. "'t, 61. 273-l ll.
228
6 The Structure and Reactivity of
Molecvles
prepared by Martin and coworkers.37 These, as well as related phosphoranes, provide

interesting insight into certain molecular rearrangements (see page 240).
Bent's rule is also consistent with. and may provide alternative rationalization for,
Gillespie's VSEPR model. Thus the Bent's rule predication that highly electronegative
substituents will "attract" p character and reduce bond angles is compatible with the
reduction in angular volume of the bonding pair when held tightly by an electronegative substituent. Strong, s-rich covalent bonds require a larger volume in
which to bond. Thus, doubly bonded oxygen, despire the high electronegativity of
oxygen, seeks s-rich orbitals because of the shortness and better overlap of the double
bond. Again, the explanation. whether in purely s-charocter terms (Bent's rule) or in
larger angular volume for a double bond (VSEPR), predicts the correct structure.
It is sometimes philosophically unsettling lo have multiple "explanations" when
we are trying to understand what makes molecules behave as they do: it is only human
"to want to know for sure" why things happen. On the other hand, alternative,
nonconflicting hypotheses give us additional ways of remembering and predicting
facts, and if we seem to find them in confiict, we have made either: (I) a mistake
(which is good to catch) or (2) a discovery!
The mechanism operating behind Bent's rule is not completely clear. One factor
favoring increased p character in electronegative substituents is the decreased bond
angles of p orbitals and the decreased steric requirements of electronegative substituents. There may also be an optimum "strategy" of bonding for a molecule in which s
character (and hence improved overlap) is concentrated in those bonds in which the
electronegarivity difference is small and covalent bonding is important. The p character. if any, is then directed toward bonds to electronegative groups. The IaUer will
result in greater ionic bonding in a situation in which covalent bonding would be low
anyway (because of electronegativity differencesP
Some light may be shed on the workings of Bent's rule by observations of
apparent exceptions to it.lll The rare exceptions to broadly useful rules are unfortunate with respect to the universal application of those rules. They also have the
annoying tendency to be confusing to someone who is encountering the rule for the
first time. On the other hand, any such exception or apparent exception is a boon to
the research scientist since it almost always provides insight into the mechanism
operating behind the rule. Consider the cyclic bromophosphate ester:
The phosphorus atom is in an approximately tetrahedral environment using four

u bonds of approximately spl character. We should expect the more electronegative
oxygen atoms to bond to s-poor orbitals on the phosphorus and the two oxygen atoms
in the ring do attract hybridizations of about 20"/. s .40 The most e.lectropesitive substituent on the phosphorus is the bromine atom and Bent's rule would predict an s-rich
n For a review, see Manin. J. C. Scit!nu 1983.111. 509-514.
For a funher discussion of ionic versus covalent bonding and the total bond energy resulting from
the sum of the two, see Chapler 9 .. Eie<:troncplivity and Hardne$$ and Sollnes.s.
In addition 10 the ellll111fllc given here, see PrOblem 6. 12.
40Qrim, S. 0 .; Plastas. H. J.; Huheey, C. L; Huheey, J . E . PhoJPhorusl911, I, 61-66.
Stnoctvre and Hybndizotian
229
orbital, but instead it draws another s-poor orbital, slightly less than 20"/. s. The only srich orbital on the phosphorus atom is that involved in the u bond to the exocyclic
oxygen. This orbital has nearly 40"/. s character! This oxygen ought to be about as
electronegative as the other two, so why the dilfereace? The answer probably lies in
the overlap aspect. (I) The large bromine atom has diffuse orbitals that overlap poorly
with the relatively small phosphorus atom; thus. even though the bromine is less
electronegative than the oxygen, it probably does not form as strong a covalent bond.
(2) The presence of a ., bond shonens the exocyclic double bond and increases the
overlap of the u orbitals. If molecules respond to increases in overlap by rehybridiza..
tion in order to profit from it, the increased s character then becomes reasonable.
From this point of view, Bent's rule,might be reworded: The p c/luru,ter tends to
concentrate in orbitals with weak covalency {/rOm eithu electronegatillity or overlap
considerations), and s charecter tends to concentrate in orbitals witlt strang
covalency (matched electrOflegativities and good overlap).
Some quantitative suppon for the above qualitative arguments comes from avera&e bond energies of phosphorus, bromine, and oxygen (Appendix E):
P-Br
P- 0
P=O
264 kJ mot-
33S kJ mol- l
S44 kJ mol-l
Bent's rule is a useful tool in inorganic and organic chemistry. FOJ example, it has
been used to supplement the VSEPR interpretation of the st ructures of various
nonmetal fluorides, and should be applicable to a wide range of questions on
molecular st ructure.
Nonbonded
Repulsions
a nd Structure
For anyone who has encountered steric hindrance in organic chemistry. the emphasis
thus far placed on electronic effects as almost the only determinant must seem
puzzling. However, the preeminence of electronic over steric effects can be rationalized in tenns of the following points: (I) Even the largest "inorganic atomic
substituent," the iodine atom, is no larger than a meth yl group (see Table 8.1 for van
der Waals radii), to say nothing of t-butyl Of di-onhosubstituted phenyl groups. (2)
The wider range of hybridizaaions, the larger variety of varying electronegalivities.
and the greater imponance of smaller molecules oil combine to enhance electronic
effects. so much so. in fact. t hat it is easy to forget nonbonded interactions in the
discussions of electron-pair repulsions, overlap, etc . in the preceding sections. BaneU
has called allen lion to the imponance of nonbon(led repulsions and to the situations in
which they may be expected to be important.l In general, the Iauer are apt to be
molecules in which a small central atom is surrounded by large substituent atoms.
Consider the water molecule, for example, witb a bond angle of 104.5". Replacing the
hydrogen atoms with more electronegative halogen atoms s hould reduce the bond
angle in terms of either Bent's rule or VSEPR-electronegativity models (rule 4 , page
217). Indeed, OF2 has a slightly smaller bond angle, 103.2". On the other hand, the
bond angle in Cl20 is larger than tetrahedrol; it is 110.8. Similarly, in the haloforms
Huheey. J. E. ,,.,,. Clwm.
42
mt. 10.
e"*"""'
Bandt. L S. J. a-t. Edll('. 1961. 4S. 7s.-767. This is anolher

d 1he principle tloaJ iC
o.map is included, anlibandina arbilals are mare clestabili:zma than the CGCTC$p()ftllina bandina
Gltilais are subiliUJoa, Nanba>dcd
are merely anocher name for dcscribina lhe foo:cd
a-up ar 1wa orbitals aRady filed
dcclrons and 1he cJest.ab;iulion lhal occun as lhe
asdlondin& orbilal rises in encfJY futer lhM lhe boftclina anc Iowen.
230
and methylene halides, HCX3 and H2CX2 , substitution of fluorine causes the bond
angles to decrease (108.6, 108.3"), but lhe corresponding chlorine compounds show
larger bond angles (111.3, 111.8").
An interesting example of this effect is isobutylene, CH2=C(CH3h. Naively we
might assume substituents on an ethylene to be bonded at 120". We have seen that
VSEPR predicts that me double bond will tend to close down the CH3-C-CH 3
angle, but how much? Bartell has pointed out that if you assume that the two methyl
groups and the methylene group can be ponrayed by spheres representing the van der
Waals radius of the carbon plus hydrogen substituents, then the short C=C double
bond naturally causes repulsions at 120" that can be relaxed if the CH3 -C-CH3
angle closes. Furthermore, it should close exactly enough to make all repulsions
equal; thus the three substituent carbon atoms should lie very nearly on the comers of
an equilateral triangle, which they do (Fig. 6.20). Furthermore, it is possible to
quantify these qualitative arguments and reproduce the bond alll!les in some repre.sentative hydrocarbons quite well (Fig. 6.21).
Bent Bonds
The overlap of two atomic orbitals is maximized if they bond .. head on." that is, with
the maximum electron density directly between the nuclei. However, small rings
exhibit ''ring strain" in the form of poorer overlap. Although rehybridization occurs
as ring size decreases, which places more p character within the ring and more s
character in exocyclic bonds, the minimum interorbital angle possible with only sand
p orbitals is 90" (pure p). In three-membered rings the orbitals cannot follow the
internuclear axis; therefore the so-called ubonds are not symmetrical about that axis
but are distinctly bent. The bending of these bonds can actually be observed experimentally with a buildup of electron density outside the ring (fig. 6.22). For example.
in 3-{(p-nitrophenoxy)methyl)-3-chlor<><.liazirine
the increase in electron density is clearly seen both in the cyclic bonds (outside the
C-N-N triangle) and in the N=N double
Fig- 6.20 Relaxation of nonbonded repulsions in a pcrfecdy trigonal isobutylene molecule to
form I 14" bond a..:te observed expcrimentaUy. (From Bartell. L S. J .
EJuc. t968. -15.
7S4. Used with permission. I
Rebxu
4'
Coppens. P. Jln-.
Int. Ed. nrl., 1971. 16, 32-40. Cameron. T. S.; Baksl>i. P. K.:
Borecka, B.: Liu. M. T. H. J . Am.
S. 1m. IU. 1889-1890.
Struclure and Hybridizatian
231
Fig. 6.21 Comparison of calculaled C-C-C bond anaJes with experimental vallles.
Calcul:ltions are based on nonbonded interoclions. The solid bar rq,rcsents a ranse of values
found inn-alkanes. (From Bartell. L . S . J .
Educ. 1968, 4S, 7S4. Used with
permis.o;ion.f
(o)
(b)
(C)
Fig. 6.22 1lle three-membered C-N-N ring in a diazirine molecule: (a) Electron density
through the plane of the dia.zirine ring. Contours are at S x J0-7 e pm-). (b) Differential
elect roo density map through the plane of the dlazirine ring showing inc:=s (solid lines)
and decreases <broken lines) or electron density upon bond formal ion. Contours are a1
4 x to- e pm- 1 No1e the build-up of electron density
the C-N-N triaf1!le.
The effects can best be seen by superimposing a transparency (as made for overhead
projectors. for example) of pan (b) over part (a). (c) lnterprewion of (a) and (b) in terms of
hybrid orbitals. !From Cameron, T . S.; Bakshl, P. K.; Borecka, B.; Liu, M. T . H. J. Am. t
Chtm. Soc. 1m. IU. 1889-1890. Reproduced with permission.!
232
6 Tlte Slnldure and Reactivity of Molecul"
Bond Lengths
Bond lengths and multiple bonding were discussed in ChapterS, and a comparison of
various types of aromic radii will be discussed in Chapter 8, but a shon discussion of
factors that affect the distance between two bonded atoms will be given here to
complement the previous discussion of Sleric factors.
Bond Multiplicity
One of the most obvious factors affecting the distance between two atoms is the bond
multiplicity. Single bonds are longer than double bonds which are longer than triple
bonds:C-C 1.54pm,C= C 134pm, CE;;C 120pm;N-N = 14Spm,N=N
12S pm, N==N
110 pm; 0-0 148 pm, o...o 121 pm, etc. For carbon,
Paulinrc has derived the following empirical relationship between bond length (D in
pm) and bond order (n):
(6.8)
This relarionship holds not only for integral bond orders but also for fractional ones (in
molecules with resona.n ce, etc.). One can thus assign variable bond orders
upon the length of the bond. In view of the many factors affecting bond lengths . to be
discussed below. it does not seem wise to attempt to quantify the bond order-bond
length relationship accurately. Nevenheless, bonds formed by elements other than
carbon show similar trends (rl8. 6.23), and the general concept cenainly is a valid one.
We have seen in ChapterS that the strenath of a bond depends to a cenain extent
upon the hybridizations of the atoms forming the bond. We should therefore expect
bond length to vary with hybridization. BentJ6 has shown that this variation is quite
regular: c-c bond lengths are proportional top character (F"13. 6.24) or, to say it
fig, 6.23 T'uJ11$tCIHI.I18SlCn

bond len&lhs as 1\Jnction
or bond order. Each oflhe
points reprcscnl$ the mean
and ranse or several values.
See Chapter 16 for
discussion of multiple
bonds in metal clusters.
Bond orders arc ploued on
a tosanth mic scale in
acc:ord with Eq. 6.8.
.!: 2SO
3t 240
i
230
220
I tO ut.D
L - - - -2..1.0--3.1..0--'4.0
Bond erda-
44
Paulina. L 'nrr NoUiro{rlrrCitrrrical Bond, 3rded.; Comdl Urivenity: ltt..ca, NY, 1960; p23'
&perimentol O.te...,ination of Moleculor Slrveture
233
Fig. 6.2.4 <ArtlOCH:albon
160
bond l<'lgths as a funcJion

of !he hybridization of !he
::=.c-("
/
(
ISO
. . ) _c...
bonding a1oms. (Data from

Bcn1, H. A . Cltrm.
IK t . 61, 275-311.1
......
I <!a
0
..,c
.,...
0
.D
llO
120
-C'C'o1-:11'
.....
another way, incrusing s cllaracter ina-eases overlap and bond slrengt.h and thus
shortens bonds.
Another factor that affects bond length is electronegativity. Bonds tend to be
shortened, relative lO the expectations for nonpolar bonds, in proportion to the
electronegativity difference of the component atoms. Thus the experimental bond
length in HF is 91.8 pm versus an expected value of 108 pm. The quantitative
shortening or bonds because of electronegativity differences and multiple bonding in
elements other than carbon will be discussed in Chapter 8.
Experimental
Determination of
Molecular Structure
X-roy Diffraction
It is impossible to present the theory and practice of the various methods of determining molecular structure completely. No allempt will be made here to go into these
methods in depth. but a general feeling of the importance of the different techniques
can be gathered together with their strengths and
For more material on
these subjects, the reader is referred to texts on the application or physical methods to
inorganic chemistry."'
X-ray diffraction (Chapter 3) has provided more structural information for the inorganic chemist than any other t echnique. It allows the precise measurement of bond
angles and bond lengths. Unfortunately, in the past it was a time-consuming and
difl"'tcult process, and molecular structures were solved only when there was reason to
believe they would be worth the considerable effort involved. The advent of more
efficient methods of gathering data and doing the computations has made it relatively
easy lO solve most struCtures.
.,. Dnao. R. S. l'hysicol MrtloodlforC/offllisu, 2nd rd.; Sai.Widers: Philadelphia. 1992. Ebswcnh, E.
A. V.; RanJcin. D. W. H.; Cralodt, S. Structwal Metlwxl1 in llt>rpk
Blackwdl: OXford. tm .
2nd ed.;
234
6 Tlle Sh'ucture and Reactivity af Malecuf..
In order to solve a s tructure by X-roy diffraction, one generally needs a single

crystal. Although powder data can provide "fingerprint" information and, in simple
cases, considerable data, it is generally nece.ssary 10 be able to grow crystals for more
extensive analysis. X rays are diffracted by electrons; therefore what are located are
the centers of electron clouds, mainly the core electrons. This has two important
consequences. First, if there is a great disparity in atomic n umber between the heavy
and light atoms in a molecule, it may nOI be possible 10 locale the light atom
(especially if it is hydrogen). or to locate it a accurately as the heavier atom. Second,
there is a small but systematic tendency for the hydrogen atom to appear to be shifted
10-20 pm toward the Blom to which it is bonded.J This is because hydrogen is unique
in not having a core centered on t.he nucleus (which is what we are sec:king) and I he
bonding electrons are concentrated toward the binding atom.
Because the locBlion of an Blom in a molecule as obtained by X rays is the time
average cL all positions it occupied while the st ructure was being determined, the
resultant structure is often presented in terms of tlrumal ellipsoids, which are probability indicators cL where the atoms are most likely to be found (see Frg. 6.25).
Occasionally. from the size and orientation of an ellipSOid, something may be ventured
on the bonding in a molecule. lf the ellipsoid is prolate (ovoid. American football
shaped), the motion of the atom is mostly back and fonh along tM bond axis, and if
oblate (curling-stone shaped), the molion is mOstly wobbling about the bond axis.
Obviously, the less the atom moves in the molecule. the smaUer its thermal ellipsoid.
In the molecule shown in Frg. 6.2.5, the carbon atoms in lrimethylphosphine and in the
phenyl rirrgs "waggle" a good deal: the atoms "locked" in the central five-membered
ring move relatively little. This is especially true of the platinum Bloms: they are heavy
and so they have less thermal motion. For someone used to "bull-and-stick" models,
this is perhaps the most confusing aspect of an ORTEP diagrnm"6 viewed for the first
Fig. 6.25 ORTEP diay.un o( comple containinc trimahytphosphine and nitrosobenzene

ligands. and two platinum atoms. NOte lhe differences in the sizes of the thermal ellipsoids
Cor C. N, and Pl. For a discussion of the types or bondifll in this complex. see Olapter 12.
(From Packetl. D. L; TrOller. W. C.: Rheinaofd, A. L . lnorg. Chtm. 198'1.16, 4309.
Reproduced with permission. I
ORTEPis an acronym ror()ak Rqe Thennal Ellipsoid f'rosnm,
used in strucnrnl .Wysis. The acronym is onm U$<d as shan Label to
ellipsoids indicate the Clltent or lherwW
of the atoms.
a dnwifll in whicJJ
hperi-ntal Det-inatian of Molecular Structure
235
time. We become accustomed to the size of an ato m being reflected in the size of its
modei---ORTEP drawings are often quite lhe opposite.
Neutron diffractio n is very similar in principle to X-ray diffraclion. However, it
differs in two imponant characteristics: (I) S ince neulrons are diffracled by the nuclei
(rather than the electrons), one indeed locates the nuclei directly. (2) Furthermore,lhe
hydrogen nucleus is a good scatterer; thus the hydrogen atoms can be located easily
and precisely. The chief drawback of neutron diffraclion is that one must have a
source of neutrons, and so the method is expensive and not readily available. X-ray
diffraction and neutron diffraction may be used to complement each other lo obtain
extremely useful resulls (cf. Fig. 12.24).
Methods Based on
Molecular Symmetry
S ince a molecule with a center of symmelry, such as one belonging 10 point groups
(n even), C.u, (n even) . D"J (n odd), Oh and lh cannot have a dipole momenl, no
malleT how polar the individual bonds (Chapcer 3), dipole moments have proved lobe
useful in distillgllishing between two st ructures. Much of lhe classic chemistry of
square planar coordination compounds of Ihe lype MA2 B2 was elucidated on the basis
of cis isomers having dipole moments and lrans isomers having none (see 0\apter 12).>
Both infrared (IR) and Raman specll'OScopy have selection rules based on the
symmetry of the molecule. Any molecullll' vibration that results in a change of dipole
moment is infrared active. For a vibration to be Raman active, thCTe must be a change
of polariz.ability of th.e molecule as the transition occurs. II is thus possible to
determine which modes wiU be IR active, Raman aclive, bot.h, or neither from the
symmetry of the molecule (see Chapcer 3). In general, these two modes of spectroscopy are complementary; specifically, if a molecule has a center of symmelry, no
!R active vibration is also Raman active.
lbere are many methods that give spectroscopic shirts. sometimes called chemical shifts, depending on the electronic environment of the atoms involved. For many
of these met hods, it is necessury to use symmetry consideralions to decide whether
atoms are chemically equivalent (symmetry equivalent) in interpreting the spectrOSCopic results. Two atoms will be symmetry equivalent if there is al least one
symmetry operation that wiU exchanee them. For example, lhe chloro groups of
(D4h) are all equivalenl since any one chloro group can be moved into lhe
posi11on occupied by another one by a C4 rotation or by a reftection (u,:or ur-1- On the
other hand. in At1 Br.,
Fig. 6.1h) lhe bridging bromo groups are not equivalent 10
lhe terminal bromo groups since no symmelry operation wilhin D'lh allows lhem to
interchange positions. Operations do exist . however , I hat inlerchange the two bridging bromo groups wilh each other and lhey lherefore are equivalent. Likewise, the
four terminal groups are equivalent because they can be interchanged by a symmetry
operation.
Perhaps more sublle is a molecule such as PFs (Ftg. 6.1 e). which has Dlh
symmelry. The lhree equatorial ftuorine atoms can be interchanged by reflection or by
rotation about lhe Cl axis. Similarly, the t wo axial atoms can be rellecled or rotaled
inlo each other. Howevct", no operation allows interchange of an axial and an equatorial ftuorine atom. Thus we have lwo sets of symmetry (and chemically) equivalent
fluorine aloms. As a consequence, we would ncx expect P-F""' bond lengths to be the
same as P- F.q bond lenaths (and they are nol), nor would we expect the five fluorine
., For fur1her
J. 0 . R.
or the use old;polc
in strueture ...
Moody. G. J.: Thomas.

t971.
ftlommts iiiiNNfoniC Cltffl'i.#ry; Edward Arnold: London.
236
6 n.e Structure and Rea ctivity of Molecules
atoms to be identical spect roscopically. The lllf NMR spectrum of PF,, however.
consists of a single doublet, indicating that a ll fluorine atoms are equivalent. This
means that: (I) all of the P- F bonds are identical or (2) the fluorine atoms are
exchanging positions faster than the NMR technique can follow. We have seen that it
is structurally impossible to have a three-dimensional arrangement of live equivalent
points in space. We are therefore led to accept the second alternative. This process of
interconversion will be discussed Iuter in this chupter.
Other spectroscopic techniques also may be applied to the resolution of molecular
structure. For now, one general method may be illustrated by the MOssbauer elucidation ofthe structure of 12CI4 Br2 By analogy with
(Fig. 6.26a), we might expect a
bridged structure with either chloro or bromo bridges (Fig. 6.261>-d). The expcrimen-
o-......,.....- -.. . . 1 .....-o
o,.
n/ " . / ' o
o,..
lol
(bl
Fig. 6.26 Some possible

structures of iodine
trihalide$. Note thai
structure (d} has a different

environment f each iodine
atom.
o......_ _,.....o......_ ,....a,

1
Br /
' o/
c,.
,,.....- 'o/ ..........
'o
c,.
lei
(dl
F'rg. 6:0
,,.,
MOssbauer spctr:t of l A
(lop) and
(bouoml.
Note spliuina of pea1t A in
I,CI,. into A and A and B

into B' in J,Br1Ct..
Presumably C' is hidden
undr a shoulder of B.
(From Pa.sJernak. M .;
Sonnino. T. J .
f'hys.
1968. 48. 1991. Rproducd
with permission.}
+t.S
+I
+O.S
Vdoeily (em s' 1 )
1.5
t.O
0.5
Vdoc:ily (cno s' 1)
Some Sionple Reoctions of Covolently Bonded Molecule s
237
tal result411 that the rwo iodine atoms ure in different environments (Fig. 6.27) rules out
the symmetrical structures shown in Fig. 6.26b, c and strongly suggesls that the
correct structure is Fig. 6.:!6d.
Sum mary o f
St ru ctural
Methods
Some Simple
Reodions of
Covale ntly
Bonded
Molecule$
Atomic
lnvet'Sion
This has been a brief survey of some of the methods available to t he inofl:'dnic chemist
for the determination of structure. Further examples will be encountered later in the
text illustrating methods. A useful summary of some of the methods of st ructure
determination has been provided by Beau ie.9 listing some of the characteristics that
have been discussed above as well as some other features of their use (Table 6.5).
One of the major differenc.e s between orgunic and inorganic chcmislry is lhe relative
emphasis placed on structure and reactivity. Structural organic c.hcmistry is relatively
simple, as it is based on digonal.
or tetrahedral carbon. Thus organic chemistry has turned to the various mechanisms of reaction as one d the more exciting
aspects of the subject. In contrast. inorganic c.hemistry has a wide variety of structural
types to consider, and even for a given element there are many factors to consider.
Inorganic chemistry has been, and to a large extent still is, more concerned with the
" static" slructures of reactants or products than with the way in which they interconvett. This has also been largely a resull of the paucity of unambiguous data on reaction
mechanisms. However, this situation is changing. Interes t is increasingly centering on
how inorganic molecules change and react. Most of this work has been done on
coordination chemistry, and much of it will be considered in Chllpter 13, but a few
simple reactions of covalent molecules will be discussed here.
The simplest reaction a molecule such as ummonia can undergo is the inversion of the
hydrogen atoms about the nitrogen atom, analogous to the inversion of an umbrella in
a high wind:
;\
(6.9)
H H
One might argue that Eq. 6.9 does not represent a reaction because the "product" is
identical to the "reactant'' and no bonds were formed or broken in the process.so
Semantics aside. the process illustrated in Eq. 6.9 is or chemical interest and worthy of
chemical study. For example, consider the trisubstituted amines and phosphines
shown in Fig. 6.28. Because these molecules are nonsuperimposable upon their mirror
images (i.e., they arc chiral), they are potentially optically active, and separation of
the enantiomers is at least theoretically possible. Racemization of lhc optically active
Pastemalc. M. ; Sonnino. T. J . Cum. l'l<y1. 1768, 4/S, 19'17-2003.

119
Beatlic, I. R. Clum. Soc. Rrv. 1975,4, 107- ISl. See abo FOOIIICIC 4$.
"'Obviously. lhe same resub can be oblaincd by clissociMina a hydrop:n alom from 1be nilrop:n :ucrn
and allowin& it 10 I'CCOITtline 10 form 1be
confip!Dtion. For a discussion ol 1hci various
compdq mechanisms lhal musa be clislquished in audyina Eq. 6.9. u wdl as values for barrier
ancl mahods ford>uinina !hem. sec Lambcn, J . B. Tupk1 Slrrtcx:ltrm. 197t . 6, 19-105.
00
Table 6.5
lor strvcturol shldiM
Comporison ol 50mt
edwtiflut
' -,
..
' Scanering, melnly by

electrons, followed by
Interference
(A - 0.01-1 nm)
diffraction
'
......
t'
,..._....,
of the tlrtct
eutron diffraction
_.,...,_
If'; ...
llllwactloe ....
EJec1ron densily map

of crystal
StMitMty
10-"s but
cry sial
-JO-l cml
averaaed over
' vibralional
motion
Scauering, mainly by
nuclei, followed by
interference
(A'" 0.1 nm)
Vector internuclear
distances
tO-lls but
cryslal
averaged over
-1 cm'
vibrational
motion
Dill'raction (atom or
molecule) mainly by
nuclei, but also by
electrons
(A .. 0.01-o.t nm>
Scalar di.stance s due

10 random
orienlation
tO- lls but

IOOPa
averaged over
(I torr)
vibrational
mo1ion
Absorption of radiation
due 10 dipole change
during rotation
(A O. l-30cm;300-l
GHt in frequency)
Mean value or ,-2

terms; potenlial
runctlon
ao- s
I0- 2 Pa
oo- torr)
Absorption of radial ion

due to dipole change
during vibration
CA- to- - to-cm)
Qualitative for large

molecules
!O-Js
IOOPa
(I torr)
JJ
Eleclron dill'raction
h -
lof
. ...
.....
,
Microwave
J
....l1,,,.
'!"I< ...
i/
Vibralional infrared
......
-t
,. ;
.......
.......... .
......_. ..! _
........ -
-'
c-Location of light atoms or

dislincllon between
&I oms of similar
scauering factor difficult
in presence of heavy
atoms
Extensively used to locate
hydroten atoms. May
aive additional
information due to spin I
on neutron leadlna 1o
magnetic scatle.ring
Thermal molions cause
blurring of distances.
Preferably only one
(small) species present.
Heavy atoms easy to
detect
Mean value or does not
occur at ' even for
harmonic mo1ion.
Dipole moment
necessary. Only one
component may be
detected. Analysis
dlfficuh for large
molecules of low
symmetry
Useful for
characterization. Some
sti\Jctural informalion
from number of bands,
position, and possibly
isotope efl'ects. All
states of mauer
,-2
...
\- Vibrahonal Raman
.
' if;;
'i' ( <A
'
Electronic
i{ .
f
1t' ...-4 ..
f.
t. . ...
...
f:
spectrometry
; t-. :
t ....... .l:
i
ji
I04Pa
Absorption
due to dipole chanee
durina an electronic
transition
(A
10-IOl nm)
Qualitative for laree

molecules
1o-1s s
tPu
(I0- 2 torr)
Interaction of radialion
with a nuclear transition
In a menetic field
(A - IOl-10' em;
3kHz lo 300 MHZ)
Detection or rraaments by
chafJCimass
Number of
mqnetlcally
equivalent nuclei in
each environment
10-'-10-9 s
IOlPa
(IOtorr(IH))
Mass number, plus
IO Pa
(lO-ll torr)
rraamentation
pattem.s
fl.
Ba:teniled X-ray
absorption fine
! structure
' (EXAFS)
Back scauerine of
photoelectrons off
lipnd.s
Radial distances,
number, and types
of bonded atoms
10- 11 s, but
Any stale
averqed over
vibrational
molion
in part. (rom Beallie.l. R. Chrm. S. R 1975.4, t07. Used wilh pennlssion.
..,
(100 torr)
(v' dependenl)
uclear
. miBilehC
resonance
...
10-" s
i'" II.'..
,,.
r!
with Qualitalive for 1atae

ehaneed frequency due
molecules
to polarizability chanee
durine a vibration
(A visible usually)
Usef\11 for
struclurallnformalion
from number of bands,
position, depolarizalion
ratios, and possibly
Isotope elf'ects. All
slates of mauer
Useful for
siiUCiural information
from number of bands
and posillon. AU slates
of mauer
Useful for
characterization.
Struclural information
from number and
mulliplieity of sianals
Useful for charaelerizalion
of species In a vapor,
complicated by
reae1 ions in
spectromeler. Does not
dilferentlale isomers
direclly. Important for
deleclina hydroeen in a
molecule
Especially useful for
melallobiomolecufes
and heteroeeneously
supported catalysts
6 Tlle Str ucture and Reactivity of Molecul..
material can take place via the mechanism shown in Eq. 6.9. It is of interest that the
energy barrier to inversion is strongly dependent on the nature of the central atom and
that of the substituenls. For example, the barrier to inversion of erhylpropylphenylphosphine (Fig. 6. 28b) is about 120 kJ mol- l. This is sufficient to allow the separation
of oprical isomers, and their racemization may be followed by classical techniques. ln
contrast, the barrier to inversion in most amines is low(- 40 kJ mol- l in methylpropylphenylamine: about 2.5 kJ mol - l in ammonia). With such low barriers to
inversion, optical isomers cannot be separated because racemization takes place faster
than the resolution can be effected. Since traditional chemical separations cannot
effect the resolution of the racemic mixture, the chemist must rum to spectrosCOpy to
study the rate of interconversion of the enanriomers. The techniques involved arc
similar to those employed in the study of fluxional orsanornetallic mol.e cules (Chapter
1.5), and for now we may simply note that for inversion barriers of20- IOO kJ mol-l,
nuclear magnetic resonance is the tool of choice.
Because the transition stile in the atomic invenion process of Eq. 6.9 involves a
planar, sp2 hybridized central atom, the barrier to inversion will be related to t he ease
with which the molecule can be convened from itS pyramidal ground state. We should
therefore expec t that highly strained rings such as that shown in Fig. 6.28c would
inhibit inversion, and this is found (14.5 kJ moJ-1). FurlJiermore, all of the effects we
have seen pceviously affec ting the bond angles in amines and phosphines should be
parallel in the inversion phenomenon. For example, the smaller bond angles in
phosphines require more energy to open up to the planar transition s tate than those of
the corresponding arnines ; hence the oprica1 stability of phosphines in contrast lo the
usual instability of most amines. In addition, the pre.s ence of electron-withdrawing
substiruents tends to increase the height of the barrier, but electron-donating groups
can lower it. Just as in the case of the stereochemistry of pyramidal molecules, the
results can be rationally accommodated by a variety of interpretations .
Berry
seudorotation
We have seen previously that in PF, the fluorine atoms are indistinguishable by means
of 19F NMR (page 236). This means that they are exchanging with each other faster
than the NMR instrument can distinguish them . The mechanism for this exchange is
closely related to the inversion reaction we have seen for amines and phosphines. The
exchange is believed to take place through conversion of the ground state trigonal
bipyramid (TBP) into a square pyram idal (SPI transition state and back to a new TBP
structure (Fig. 6.29). This process results in complete scrambling of the fluorine atoms
at the equatorial and axial positions in phosphorus pentafluoride, and if it occurs faster
than the time scale of the NMR experiment (as it does), then all of the fluorine atoms
(a)
fig. 6.28 Chital amincs and phosphines.
Some Simple Reactions of Covalently lande d Molecule s
241
appear to be ident ical. Because it was first suggested by Berry,,. and because, if all of
lhe sUbstiruents are lhe same as in PF,, the two TBP arr.111gements (Fig. 6.29) are
related to each other by simple rotation, the entire process is called a Berry
pseudorotation. Note that the process can take place very readily because of the
similarity in energy between T BP and SP structures (page 223). In fact, the series of
five-coordinate srructures collected by Mueuerties and Guggenberger, which are
intermediate between TBP and SP geometries (Table 6.3), effectively provides a
reaction coordinate between the extreme structures in the Berry pseudorotat ion.
The exchange of fluorine atoms in PFs is too rnpld to monitor with NMR spectroscopy. The atoms in some other molecules exchange more slowly, especially at
lower temperatures. For example,
is expected to be a trigonal bipyramid with
two apicophilic fluorine atoms in the axial posi tion s, and two chlorine atoms and the
third ftuorine in equatorial positions. At temperatures of - 22 c and above, the
resonance of ftuorine is observed as a single doublet (Fig. 6.30a). However, if the
tempernture is lowered to -143 "C, the two axial fluorine llloms can be distinguished
from the single equatorial fluorine (Fig. 6.30<1).
All three 19f nuclei (I = il are split by the liP nucleus (1 = il with a coupling
constant of JP-F - 1048Hz. At - 143 "C this produces a downfield doublet (8 -67.4)
for the
atoms and an upfield doublet (841 .S) for the equatorial fluorine atom. The
single equatorial fluorine atom splits each component of the doublet of the two axial
fluorine atoms into another doublet (2nl + I; n - I) with Jp_p - 124Hz. ln the same
way the doublet pallem of the single equatorial atom is split into triplets (2nl + I, n =
2) by the two altial fluorine atoms. The overall intensity of the axial fluorine resonance
is twice that of the single equatorial fluorine. Also, the weighted average c:i the
chemical shifts at -143 c [2 x ( - 67.4 ppm) + I x ( + 41.S ppm)) is the same as that
at -22 "C [3 x (-31.1 ppm)) indicating that the s tructure does not change on
warming, even though the fluorine exchange accelerates. The fact that phosphorus-fluorine coupling is preserved on warming indicllles that there is no inter
molecular exchange, but that the coalescence of the spectrum at higher temperatures
is t he result of an intramolecular rearrangement.
c..
D,.
Fog. 6.29 Berry pseudorotoricn in a pentavalenl phosphorus compound.
' 1
Beny, R. S. J . CMm. l'hys. t960,1l, 933-938. Forrccenl

Cotbridce, 0 . E. C. l'ltcJJpltonu: An OU1/i111t of Ill Chtmis try, Bicdwmistry cmJ Tc-hnology, 4th
cd.; Elsevier. Amslerdam, t99(); pp 994-1003; CaveQ, R. G. In l'hMpltor111-11 NMR Sparos<Opy
in
AnG/y1is; Verltade, J. G.; Quin. L. 0 . Eels; VCH: Oca1idd Beach. FL. t987:
a.a.>ta 7.
242
6 The SlnlclVre ond Readlvity of
(b)
-109"
t<l
-12.,.
(d)
- 143"
H-
fig. 6.30 19f NMR specu11 or a solution of PCI:F, in isopenlane M various aempentures. AU
rL the lb>rine
are cloubleas from
coup&na. (a) AI -22 "Conly a sinale
doublea is observed, indieatina aha! all of the fluorine atoms are equivalau. (b) AI - t09 "C
thi$ resonance disappears. (c) AI - 127 "C IWO new abS"ppions :lflpear. (d) AI -143 "C IWO
lypes of lluorine uoms are seen: a doublet of cloublels al low field (two uial Fs) and a
double! of triplets at biah6 field (one equ111orial FJ. (from Holmes, R. R.; Caner. R. P. lr.;
Peacrson, G. E. '"0<6 Chrm. 1964. J. 1748-t?$4. RcllO"oduccd wilh pennission.)
Substitution of alkyl groups on the phosphorus atom provides some interesting

effects. If a single methyl group replaces a fluorine atom. it ocaJpies one of the
equataial positions as expected and 111pid exchange or the two axial and the two
equatorial fluorine atoms is observed, as in PF,. If two melhyl groups are present,
the molecule becomes rigid and there is no observable exchange among
the three remaining fluorine atoms. This dramatic chance in behavior appears to be
attributable to the intennediate which is fonned. shown in Fie. 6.:!9. In t.hc:
pseudorotation of CH1 PF4 the methyl croup can remain at position E 1 and ahus remain
in an equalorial position bolh before and after the pseudorotation. In contrast, in
(CH1 ) 2PF1 one of the methyl groups is forced to occupy either 2 or 1 : therefore.
after one pseudorotation it is forced to occupy the energetically unfavorable (for a
substituent of low electronegativity) axial posirion. APP&rently the difference in en
ergy between equatorial and axial substitution of the methyl group is enouch to inhibit
the pseudoro!ation.
This difference in energy can be shown dramatically in the sulfurane
Some Simple Reactions of Covalently Bonded Molecules
243
This molecule has an approximately TBP elecrronic structure and is chiral. However,
p()(entially it could racemiz.e via a series of Berry pseudorotations.52 That it does n()(
do so readily. and is therefore the first optically active sulfurane to have been isolated,
has been attributed to the fact that all racemization pathways must proceed through a
TBP with an apical lone pair.sl As we have seen in the preceding chapter. there is a
very strong tendency for the lone pair to seek an equatorial site. The reluctance of the
lone pair to occupy an apical site appears to be a sufficient barrier to allow the
enantiomers to be isolated.
The question might be asked: Are thece similar mechanisms for changing the
configuration of molecules without breaking bonds in molecules with coordination
numbers other than 3 and 5? The answer is "yes." One of the most important series of
inorganic compounds consists of six-roordinate chelate compounds exemplified by the
tris(ethylenediamine)cobalt(lll) ion. Because of the presence of the three chelate
rings, the ion is chirnl and racemization can take place by a mechanism that is closely
related to atomic inversion or Beery pseudorotation (the mechanism for six-coordination is termed the "Bailar twist"; see Chapter 13).
Nucleophilic
Displacement
The crux of organic mechanistic stereochemistry may be the Walden inversion, the
inversion of stereochemistry about a four-coordinate carbon atom by nucleophilic
attack of. for example, a hydroxide ion on an alkyl halide. Many reactions of inorganic
molecules follow the same mechanism. In contrast, the dissociative mechanism of
tertiary halides to form tertiary carbocatanion intermediates is essentially unknown
among the nonmetallic elemems silicon, germanium, phosphorus, etc. The reason for
this is the generally lower stability of species with coordination numbers of less than 4,
together with an increased slability of five-coordinate intermediates. This difference is
attributable to the presence of J orbitals in the heavier elements (Chapter 18).
The simplest reaction path for nucleophilic displacement may be illustrated by the
solvolysis of a chlorodialkylphosphine oxide:
We would expect the reaclion to proceed with inversion of configuration of the

phosphorus atom. This is generally observed, especially when the entering and leaving
groups are highly electronegative and are thus favorably disposed at the axial positions. and when the leaving group is one that is easily displaced. In contrast, in some
cases when the leaving group is a poor one it appears as though front side attack takes
place because there is a retention of configuration.S4 In either case, the common
" ()(course. &here are 01her poten&iol mechnnisms for racemization. If there
trace o( free aion, an SN2 displaccmcnl m.igh1be possible, or merely a simple SNI dissocialion of the Cl 31om and
r:1ccmwuion. Ncilher of thC$C reactions a ppears 10 l8l<e place cilher.
n Marlin, J . C.; Ballhazor. T. M. J. Jim. C!wm. Sot. 1977, 99. IS2-162.

_..For a discussion of lhe various possibililics. see Tobe, M. L lncf'1lonic RrtiOII
Thomas Nekon: London, 19n: pp 25-37: Katakis, D.: Cordon, G. M'chonisms of Inorganic
RroctiottS: Wiley: New York. 1987: pp 190-19t.
6 The St..,cture and Reactivity of Molecules
inversion or the less common retention. !here is a contrast with the foss of stereochemistry associated with a carbocatanion mechanism .
The stability of five-coordinate intermediates also makes possible the ready
racemization of optically active silanes by catalytic amounts of base. The base can add
readily 10 form a five-coordinate intermediate. The Iauer can undergo Berry pseudorotation with complete scrambling of substituents followed by loss of the base to yield
the racemized silane .
.
'echanisms
Most of the reactions the inorganic chemist encounters in the laboratory involve ionic
species such as the reactants and products in !he reactions just discussed or those of
coordination compounds (Chapter 13). However, in the atmosphere there are many
free radical reactions initiated by sunlight. One of the most important and controversial sets of atmospheric reactions at present is that concerning stratospheric ozone.
The importance of ozone and the effect of ultraviolet (UV) radiation on life has been
much discussed . Here we note briefly that only a small portion of the sun's spectrum
reaches the surface of the earth and that parts of the UV portion that are largely
screened can cause various ill effects to living systems.
The earth is screened from far-UV (extremely high energy) radiation by oxygen in
the atmosphere. The UV radiation cleaves the oxygen molecule to form rwo free
radicals (oxygen atoms):
02 + hv (below 242 nm) -
o-
o-
(6.11)
The oxygen atoms can then attack oxygen molecules to form ozone:
o- + 0 2 +
M -- 0 3
(6.12)
+ M
The neutral body M carries off some of the kinetic energy of the oxygen atoms. This
reduces !he energy of the system and allows the bond to form to make ozone. The net
reaction is therefore:
(6.13)
This process protects the earth from the very energetic, short-wavelength UV radiation and at the same time produces ozone. which absorbs somewhat longer
wavelength radiation (moderately high e.nergy) by a similar process:
0) + hv (220-320 nm) - - 02 +
o-
(6.14)
The products of this reaction can recombine as in Eq. 6.12, in which case the ozone
has been regenerated and the energy of the ultraviolet radiation has been degraded to
thermal energy. Alternatively, the oxygen atoms can recombine to form oxygen
molecules by the reverse of Eq. 6.11, thereby reducing the concentration of ozone. An
equilibrium is set up between this destruction of ozone and its generation via Eq. 6.13
and so under normal conditions the concentration of ozone remains constant.
The controversy over supersonic transports (SSTs) of the Concorde type revolves
around the production of nitrogen oxides whenever air containing oxygen and nitrogen
passes tlv"ough the very high temperatures of a jet engine. One of these products,
nitric oxide, reacts directly with ozone. thereby reducing its concentration in the
stratosphere:
(6.15)
Some Simple Reaction of Covalerttly Bonded Molecules
245
f\lnhermore, nitrogen dioxide formed in Eq . 6.15 or directly in the combustion

process can react to scavenge oxygen free radicals and prevent their possible recombinarion with molecular oxygen to regenerate ozone (Eq. 6.12):
o- - - NO + 0 1
N02 +
(6.16)
Note that a combination of reactions (Eq. 6. 15 and 6.16) results in the net conversion
of ozone to oxygen:
(6.17)
and that the nitrogen oxides, either NO or N02 continuously recycle and thus act as
catalysts for the decomposition of ozone:
(6.18)
The cunent controversy revolves around the extent to which nitrogen oxides,
NOx would be formed by SSTs and how much the ozone concentration would be
affected.55
The ozone question is complicated by the fact that other chemicals are implicated
in its destruction. Chlorofluorocarbons were formerly widely used as propellants in
spray cans, and they continue to be used as refrigerants.j(, They are extremely stable
and long.Jived in the environment. However, they too can undergo photolysis in the
upper atmosphere:
(6.19)
The chlorine free radical can then interact with ozone in several tlilferent ways
analogous to the NO,.. At mid-latitudes the reactions are
Cl' + 0 3
ao
o- -
00' + 0 2
(6.20)
a + o!
(6.21)
for a net reoction of:

(6.22)
with regeneration of the monoatomic chlorine. The chlorine thus acts as a catalyst,
and present evidence indicates that the a cycle may be three times more efficient in
the destruction of ozone than is the NO,. cycle.s7
ox
H . S .; Kiooison, D. E.; Wucbble$. D. J. J .

1989, 94, 16JSI-16363.
Manahan. S. E. EnllironiMnlal Chnnistry, Slh ed.; Lewis: Olelsea. MI. 1991.
,. The U.S. wil cease produclion of ozone..tq,leling c:hlofollUO<'()CaJbons by lhe end clt99S.
JS Jobns10n,
Eng.
1992, 70(6). 7-13.
" A rcc.enl "'port SIJ&8CSIS !hal NO;, acluaUy prolc:C(s ozone by sc:avensilll!lhc much mcrecleslruaive
CIO: NO, + CIO ___. CIONO,.
Eng.
t992, 70(2), 4-5.
246
6 T11 Structure and Reactivity af Molecules
The process responsible for the

hole" over Antarctica is thought to be
similar, though it may be heterogeneous. taking plate on ice parlitles.'8
00' + Oz]
2(CI' + 0 3 CIO' + CIO' + M ---+ (00)1 + M
cao)2 + h" -
+ aoo
CIOO' + M --+ Cl' + 0 2 + M
Net:
Problems
20, -302
(6.23)
(6.24)
(6.25)
(6.26)
(6.27)
6.t Draw uwis structures for the followirc molecules and predict lhe molecular geometry:
L
BCJ,
b.
c. Sn8r4
d. TeF6
e. Asf1
l. XeO,
6.2 Draw Lewis struaures for the followirc moleC111eS and pn:dict the molecular aeometrY
includina expected distortions:
a. TeO.
b. JO:i
c. OF1
d. SO,
e. XeF,
r.
C XcO,
h. OO,F1
XeF4
6.l Wh:U is the sjmplcst reason fbr' believina that molecular Slructure is more o(len governecl
by BP-BP/BP-LPil.P-LP repulsions ll'an by lhe van der Waals repulsions of the nonbondin& electrons on the subsdn>ent atoms?
6.4 Use Eq. 6.1 to derive the bond al1JI)es in sp, spl, and spl hybricl ortlitals.
6.5 Assuming that the ortitals are direaed alona the intemucleot axes (i.e. , the bonds are not
benll use Eq. 6. 1to calculllle thep character in the bondsofNH 3 The bond angle in NH1 1s
107.s''. What is the p character of the lone poir?
6.6 The bond an&Jes in the lluoromethanes are:
H-C-H
110-112"
111.9 ::!: 0.4"
F-C-F
108.3 ::!: 0. 1"
108.8 ::!: o.n
a. Calculale the s character used by the c:ubon uom in the orbitals directed to the
hydrosen and ftuorine uoms.
b. Discuss the results in terms of Bent's rule.
6.7 Show in a qualitative way why thee-.y levds of AH 1 in

6,16 increase or decrease in
the way lhey do upon bendina the molecule. Allempt 10 account for small and Jarxe
changes.
'"Zurer. P. S. CM.n. En,r. Nn.s 1990, llatll. U- 16.
Probl-
247
6.8 Consider !he f"'e radicals CH) and CFj . One is planar, the other pyramidal. WIUch is
which? Why?
6.9 Group VIA ( 16) tetrol!uorides
as Lewis acids and form
CsF- + SF. ___. Cs[SF,)CsF- + SeF. -
(6.28)
Cs[SeF,r
(6.29)
CsF- + T e F . - Cs[TeF,J-
(6.30)
Predict the scructures of these anions.

6.10 F rom
6.23. derive an equation for
analogous to Eq. 6.8 for carbon.
6.11 a. Pre<tict the carbon-<:art>on bond lenJilh(S) in benzene.
b. Predict the cazbooH:atbon bond lenglh(s) in buckminslerf\Jtlerene (f"IB- 3.33).

6.12 Consider the molecule CH,C..CH . Applyina Bem's rule in its classical form, predicl
whether the bond angles, H-e-H. are sreater oc less than 1091. Considerina the
arauments on overlap on page 228. predict aaain. (The experimental result i.s given by
Costain. C. C. J . Chem. l'hys. 1958, 29, 864.)
6.13 Consider the molecule CIF,O, (with chlorine the central atom). How many isomers are
possible? Which is the moststable? Assign point STOUP clesi$nations to each of the isomers.
6.14 The structu"' for AI;,Br6 (Fig. 6. lh) is :ISSUmed by both AI:Br6 and Al:CJ. in the gas pllase.
In the solid. however. the structures can best be described as closest packed arrays of
halosen atoms (orions) with :oluminum atoms (or ions) in tetrahedral or octahedral holes. In
solid aluminum bromide the aluminum atoms are found in paifll in adjacenl te.trahedral
holes. In solid aluminum clioride. aloms a"' found In one-third of lhe octahedral holes.
a. Oiscuss
two s1ruaures in termS of an ionic model for the solid. What factors favor
or disfavor this intaprelation?
b. Discuss these two structures in terms of covalent
in the solid. What factors
favor or disfavor this interpreuuion?

6.15 Obtain the covalent and van der Waals radii of phosphorus and the halogens from Table
8. 1.
a. Show that for an assumed bond al1flle of 109! in the phosphocus trihalides there must be
wan der Waals contacts among the halogen atoms.

b. Show that because of the concomitant increase in both covalmt and van der Waals
radii, the repulsion between the haloaens does not become wonc as one prOCfesses
from PF, to PI,.
6.16 One of the few phosphorus compounds that exhibit square pyramidal geometry is shown in
Fig. 6.3 I. Rationalize the preferred geometry of SP over TBP in terms of the presence of
the four- and
rinas. (Holmes. R. R. J. Am. Clrem. Soc. 1915. 97. S319.)
6.17 Consider the cyclic compounds I and II. In I the rapid exchansc of the l!uorine atoms is
inhibited just as it is in (CH,):PF,. However. exchange in II is very rapid. Suuest a reason.
F
II
"Christe, K. 0 .; Curtis. E. C.; Schack. C. J. ; Pitipovich, 0. lnorg.
1971, It, 1679-1682.
248
6 The Strvcture and Reactivi ty af Molecules
Fig. 6.31 Square pynmid:ll dioxo-A'-phosphane with fi- and four-.m embered rings. (From
Howanl. J. A.; Russell, D. : T rippel!, S . CMm. Cummun. 19'73. 856-857. Reproduced wilh
pc:rmiaion.l
6..11 Suagestlhe mosllikdy 51eROChemislry
the followina compound:
or
or the phosphinatc ester rcsulti na from ethanolysis
too"
6.19 Predict the acomctric$ of (CH,):P(CF,I, and (CH,))P(CF,)J. Do you upcct these molecules to undergo pscudurotation? Explain. (See The, K. 1.; Cavell, R. G .
Cummun.
1975, 716.)
6.20 In an p'd hybridiud phospbonis a1om in a TBP molecule, will the alom have a
elec:tronq alivity when bondina throu&ll equa1orial or uial ortilats? Explain.
6.21 Eartier(page 212) it WUSialed lhalthe repulsive efl'c cl s of a lOne pair and a doublybooded
oxygen alom in VSEPR lheory were very similar . Discuss qualitalive and quanlitative
differences !lull you feel should exist. (Sec C hrisiC K . 0.: Oberhamm<r, H. lnorg.
1981. 20. 296.)
6..22 Predict and say as much as you c::>n about I he probable suuaurc of solid InCl. Br r:tv({ul!
(Hint: Why do you lhin k this problem was included in this chapter ralher !han in Chapler 4?)
6.23 Consider F"c. 6 .32 which is an eleclron dcosily concout" m11p of the sodium
crystal.
1his cli..,.am in 1erms o( cverythina that you know aboutlhe 1truc:turc ot solid
sodium c)'lll"li<k.
Pro&lems
.....
I
'
249
Fig. 6.32 Oiffen:ntial electron cleflsity mup ol cryslalline sodium cyanide. NaCN. Solid
contours indicate incn:ased dec:lron cleflsity upon compound fonnation from the aiOms,
dashecl contours n:pn:sent decreased electron cleflsity. lfrom Coppens. P. Angrw. Chrm.
Int. EJ. Engl.
16, 32.)
tm.
6.2A ldenlify the symmetry elemenls ancl operations in the

and ions shown in the
fiaun:s lis1ed below. Detcnninc 1he appropri:ue point aroup for each molecule and ion.
a. 6.4
b. 6.S
e. 6.6
d. 6.7
e. 6.8
f. 6.10
1: 6.11
... 6.18
6.25 Calculate the hybridiuJion of the cal1lon and nit rosen a1oms in f'l$. 6.22.
6.26
Considc:rina the molecular orbital diagram of carbon monoxide (F'oa. S.20) and the diSC:U$sion conc:ernif1! hybridiz.aaion and energy (pages 225-227), predict which end ol the
carbon monoxide molecule will be.the more basic (i.e ., will donate electrons more readily
and fonn 1he stronacr. direct covalent bond).
6.7:1 Consult the molecular orbit Ill diosnm in
rg.
6.16 and predict whether BH, will be linear or

bent. What would you predict for the excitecl state configur:11ion,
6.2ll Refer to the molecular orbital diasnm for NOi fn Fig. S ..J I. Walsh <ingmms. similar to
those in roa. 6.16. predict thai the HOMO (o1) becomes more stable as theO-N-Obond
2SO
6 The Str01ctur and Reactiwily of Moloculos
angle llecrenses. Bond angles for NO;, NO:. nnd N0; are 11!0'. 134". un.J
livcly. Account for this 1rend.
11s. respec-
6.29 How muny sels of symmetry equivalcnl n10m nrc found in the following molecules?
a. CIF)
b. SF4
c.
d. Mn04
e. B:H
r.
g.
co;-
(D,,)
naphthalene. C 1uH
h. A 86 (D,,)
6.30 Figures 6.4b and 6.7a illuslrate unobserved bul possibl" Slruclurcs for SF. and ICI; .
Assign poin1 group symm..1ries 10 1hese hypolhelical s1ruc1ures. Would lhe difference in
symmetry alfecl lhe spe<:lroscopic propenies?
6.31 On
2JS lhc Slalem<nl is made 1ha11he.r e nrc Olher symmetry operruions which exi$1
1ha1 illustrrue I he equivalence of 1he bridgina bromo groups. Give an example.
6.J2 Aloms of molecules which are chemically nonequivale.n l are abo mqnelically nonequivale.n l and wih . in general. give rise to differcnl NMR chemic-.d shifts. Sometimes
atoms may be chemically equivalenl. bul a11he same lime be magnetically nonequivalem.
A1oms arc magnetically equivalenl if 1hey couple equally to all Olher atoms in the molecule.
For example. in methane each of I he four hydrogen u1oms couples to uc an..llo each o1her
in exaclly lhe same way and 1hey arc lherefore maanetically equivalenl (as well as
chemically cquivalenl). In trans-C1 H,F,. however. a fluorine aJom trons 10 hydrogen
couples 10 i1 dilfercmly lhan a fluorine atom which is cis. As a resull. even !hough lhe Jwo
fluorine aloms arc che.m ically (symmelry) equivalenl.lhey are magnelically nonequivalenl.
as arclhe 1wo hydrogen atom.. in NMR lcnns. we would say lhDIJhe trtms-C,H:F:
AA'XX' ra1her lhun an A:X: spin system. and 11ult ils NMR speclrum would rcflecl I hal
complexily. Refer 10 Problem 6.29 nnd de1erminc which atoms of cuch molecule or ion
magnelically equivalent.
6.JJ The slructures of all of lhe mixed In
a l - SI
(I'CI.F, _.,( an.!
chlorofluuroursancs (AsCI. Fs -.1 lulve reccmly been determined. Before reading the
experimental results. predict these s1ruc1ures.
6.34 Methyl nne! lrifluoromcthylsulfur chloride we.r e fluorinated wilh silver difluoride.!
-...,-.,...::C,=::f':..,"""--+ (II
(6.2lll
C F,SCI
(6.291
Elcmcnlal :111alysis of 1he producL save:"'
Ill C =
12) C
2.11"/.. S = 30.11"/.. F 54.11"/.:

F
72.!"/..
Predicl lhe molecular s1ruc1ure1 of the producls as complclely us possible. Name lhe
producls according 10 IUPAC nomc:rn:l:uure.
""In IUPAC nomenclature. a " phosphanc" is normally a derivalive or what we ordinarily call
"pha<phinc... PH,. Penlavalent derivative,; of I he hypolllclical PH5 (pha<plloranel are labeled
Similorty. dt:rivalives ol H:S woukl be sulfancs. and 1hc U:lravalciU and hexavalent derivatives
would be lobeled A und A. respccJively.
1
Minkwit%, R.; Prenzel. H. ; Schardey. A.: Obcrhu!MIC1". H. lnur11. Ctwm. 1987. 16. 2730-2732.
Macho. C.; Minkwitt. R.: Rohrmnn. J .; Sieger. 8 .; Wlllfel , V. : Obert.ammcr. H . lhlJ. 1986, 2S.
2828-283S.
62
Downs.A. J .;McGrndy,O. S.: Barnfoeld.E. A.;Rankin, 0 . W. H.;Robcruon. H . E. ;Boggs.J . E .:

Dobbs. K. 0 . ln<Jrl/. Chrm. 1989. 28. 3286-3:!92.
analys.:s, but lhey arcljiven here !colculalcd on the bmiis oft he
empirical formulas) IO aid in lhe solution of 1his problem.
) The aulhors did 1'101 report
.JS In the openina paracr:lph of Chapter 3 the statement was made that "frequenUy lhe most
symmetrical molecular structure is the 'prefe.r able' one." But in that same chaFter we saw
that Xe F. is square planar, 11(/f tctrahedrol. which some theoreticians had argued for
because of the hiJher symmetry of the Iauer. Other exceplions have been discussed in lhi$
chllpter. Rationalize these apparent paradoxes .
originnl inveSiigators of the diuirine compound shown in fig. 6.22 claim that the
following features cnn be found in that fiaurc:
.3(; The
(a) bent bonds in the C-N-N trianale ;
(b) the N-N double bond;

(c) the arenter electronegativity
of nitroaen compared with carbon;
(d} the presence of lone pairs on the nitroaen atoms:
of the diazirine tina. 110r should

Note the difference of an order of mqnirudc between lhe
(e} the absence of C2 symmetry in the electron density
such.,,.,.,,,
contours in (a) and (b).

ConfliTII each of these observ.uions.
Chapter
7
The Solid State
I n previous chapters we have seen how simple bonding models (the electrostatic one
for ionic compounds, various meories of covalent bonding. partial ionic and covalent
character, etc.) can be applied to the chemical and physical propenies of compoonds
of interest to the inorganic chemist. Of course, there are other imponant faclors such
as dipole moments and van der Waals forces that inlluence these propenies, and we
shall encounter them later. ln this chapter we slloll examine examples of the solids
held togelher by ionic or covalent bonds or mixtures of the two. Cryslals held together
by predominantly ionic forces (e.g., magnesium oxide, which has the NaCI structure,
see
4.1) and those held together by purely covalent forces (e.g., diamond, see Fig.
7 .I) are surprisingly similar in their physical properties. Both types of crystals are
mechanically strong and hard, are insulators, and have very high melting points (Mg()
= 2852 c. diamond = 3S.SO
Neither type is soluble in most solvents. The
conspicuous difference between the two types of crystals is that there are a few
solvents of high permittivity that will dissolve some ionic compounds (water is most
notable, but see Chapter 10). The second difference is that these solutions as well a.s
o.
Fig. 7.1 Unit cell or the struclllre ol cJiamond (carton). Note the tcltahedral ($pi)
con/icurnlion ab<lul each Mom. Cf. Fia. 4.2b. (From Ladd. M. F. C.

In SofiJ SrarL
252
Ellis Horwood:
1979. Rqwocluccd wilh
and Bon4"JIIg
n.. Structu,.. of Complex Solids
253
the molten ionic compounds conducl electricity, but that is not a property of the solid
ilself.
The Strudures of
Complex Solids
Chapter 4 considered the topic of simple ionic compounds such as NaCI, CsCI, CaF2,
etc . as well as the concepts of tetr.thedral and oclahcdral holes in closest packed
lattices, the idea of efficiency in packing. and the radius ratio rule. Chapters 5 and 6
discussed covalent bonding and the struct ure of molecules. These ideas are summarized and illustrated in Fig. 7.2 (carefully correlale the parts and processes in the f1:ure
and legend). In add ition, the drawings in this figure should be of help in visualizing
various structures by showing the different methods used by chemists to depict atoms
and ions.
.
Given the diffiaJ!ties and exceptions that we have seen with the radius rntio rule,
we might despajr that any predictive power was available to the inorgl!Bc chemist
studying complex crystal structures. If simple Mx- compounds violate the radius
ratio rules as often as they do (see
4. 18), how is the seochemist to deal in a
rational way with the structures of minerals like olivine (Mg:zSiOJ, spinel
and other silicues and aluminosilicates con taining a variety of metal ions? These
minerals fonn most of the earth's crust and mantle (see Chapter 16) . In addition to
being important minerals, some of these compounds are important in the laboratory as
well. The class of compounds culled spinels played on important early role in the
development of crystal field theory (see Olapc.er I I) . The current intensity of imerest
in high-temperature superoonductors centen on mixed metal oxides with structures
similar to the minernl perovskite (see pa;e 285).
There are various ways of looking at structures of this sort. One may fonnulate
them as silicate anions with isolated tetrahedra or linked into rings, chains, sheels, etc.
This viewpoint wiU be pursued further in Chapter 16. Alternatively, one can view
them as closest packed structures, in the case of olivine as Si.. ions occupying
tetrahedral holes and Mg1+ ions (or
ions by isomorphous replacement) in
octahedral holes in a hexagonal closest packed array of o xide ions (Fig. 7.3). But
considering the diffiCUlties encountered with the radius ratio approach, one may well
ask: " Is it possible to make accurate predictio ns?" Fo rtunately. the answer is "Yes."
The chief difficulty with the rndius ratio approach is that it is based purely on
geometric considerations, not chemical ones. If we include chemicnl facton, such as
partiul covalency. our predictive pOWer Is considerably enhanced. There are several
approaches to the problem, but o nly two will be men lioned here. The simplest is a
purely empirical appr-oach, and like so many methods in inorganic chemistry its
strength lies in its experimental basis: Possible unknown errors and hidden factors are
built into and accommodated by it . One takes a list of known structures of a given
general formula, say
(where A is a metal and B is a hi&her valent metal or
nonmetal). The radii of A and B are ploued apinst each other along two coordinate
axes. This is the graphical equivalent of looking at arithmetic radius ratios. In the
resultant structure field map (Fig. 7.4) it is fou nd that similar structures cluster
together. Tile olivines cluster around 90 pm for A
= 86 pm, 'F,... = 92 pm) and
40 pm forB (rsr = 40 pm). In contrast, the spinels cluster around rA .. r 8 - 6G-90 prn
(rAJ' = 68 pm).
A structure field map is remarkably accurnte. Thar exceplions do occur , usually
on the borders of the fields, should not be surprising. Serious erron are relatively rare.
Cl Cl
I/
/I
CI - No- CI
Cl
Cl
(d)
(I)
F
(p)
(q)
Fig. 7:1 Cieornaric relationships and intm:onvcrsiom (1 - 16) amona variou.\ molecules
tauicu (a-r): A "real'' sulfur hexafluoride molecule (a) is transformed (I) inlo a spncc-fillil1tl
model (b), which is tr:lllSformcd (2) into a "stick-and-ball" model (c) of SF. The SF.
molecule is symmetrically identical ()) to the hypolhetiaii(NaCtJ'- ion ld), which is a
portion (4) of the NaO lanice (e), which mooy be de.p icted (S) by the unit cetl of NaCI shown
as a "see lhroush" lallice (f), or de.p icted (6) as a space.fillina model (8), The unit cell (f,a)
may also be depicted (6') wilh fractional atoms to show the actual number of atoms per unit
cell (h). The unit cell is (7) pan of the extended lanice (i). Removal of the c.hloride ion
nearest the viewer (8) reveals an undef'lyi111
set of three sodium ions lyina on top
of a triangular set of six chloride ions (j), Removal of lhese three sodium ion$ and six
c:hJoricle ions (9) reveals a trianllle of ten sodium ions lyi111 on top of a trianllle of fiOeen
254
I/
/I
et
Ct- Na -Ct
a a
(c)
(f)
l6'
J1
(II)
Ja
(il
Fig. 7.2 (Continued)

chloride ions (k). The fifteen chloricle ions form ( 10) a closest pocked
of ions (I).
Compare Ill with Figs. 4. 12 and 4. 14. Taking (II) a ponion (m) of the previous array provides
(12) a tetrahedr.ll hcle (n) oc (13) an oclahedr.l! hole (o) de.pending upon the covering atoms.
Adding a second clo$est packed layer of three ions forms ( 13) an octahedral hole. There is a
C) axis
to the planed the paper(m:lrked A). Addition (14) cl:aeometric lines
shows the octahedral symmetry (p), and the s tructure may be convened (IS) into an
octahedron {q) as in SF6 which is identical to the stick-and-ball oclahedr.l! model (c) seen
previously. Likewise the formation of a tetrahedntl hole can be shown (12) by addition c( one
81om on top 10 JJive a tetrahedr.l! space-lillins model (n) whiCh. in nwn may be convened (16)
to a "real" molecule of electron clouds (r).
25S
256
7 The Solid Stale
Key:
M&
O, oop C.,...
SioboveO
:: Si
Ag. 7.3 Slroclure dan olivine. Mg,SiO po<trayed lhree WBY$. Lefl: Discrele si<f.ldrahedra and Mi+ ions. Cenrer: Nelwork of Mg-Q iluSinlling lhe exaendcd s1ruc1ure.
The Si a&oms have been omiued for clarity. Righi: Mg! ions in an hcp atr.ly d oxide ions.
The Si a10ms have been omiued. Can you find lhe lelrahednll holes 1ha1 they occupy?
[Modified from Wells. A. F. Strllctura/ Inorganic Chrmistry. Slh ed.; Clarendon: Oxford.
1984. Reproduc:ecl with permission.)
180
11- K,S04
K2NiF4 1tcvctun
No,so. (V)strucwro (th<lwditc strucnm)
180
Stz PbO IU\Idure
+ Olivine sl.NCUire
0
Phenedte structure
Spinel SINC1ure
CoFc1 0 4
81A.lt04 J&Nctwe
t&ructurc
Md ftlalcd dNC:J\Ifa
40
80
80
100
120
140
180
180
lonkradius(r8 ) i n p m -
Fig. 7.4 Saructure tleld map for A,BOt comvounds as a (unction of calion size. No1e 1hal
only the more common structures are plolled. Each point on Ihis plol represems at leasl one
compound having the indicaaed saructure and size of cations A(rAI and B(ra). !From Muller.
New York. 1974.
0 .; Roy. R. Thr Mqjor Trrnary Srrllctural FamUirs;
Reproduced wilh permission.!
The
of Complex Solids
257
but three spinels-sodium molybdate, sodium WflGStale, and silver molybdate-liill

well outside their field.'
Once we have established the fields shown in Fig. 7.4, we can use the map as
follows: If we discover a new mineral with rA = 90 pm and r 8 z 30 pm. we should
expect it to have the same structure as the mineral olivine,
but we
should not be too surprised if it turned out to be isomorphous with thenardite,
.
A second structure field map is shown in Fig. 7.S. This is a much more ambitious
and generalized undertaking, since t.he oxidation states for species A range from + I to
+ 4 and for B from + 2 to + 6. with X 0 or F. By combining such a large number of
compounds and somewhat oversimplifying the resultant diagram, we lose some accuracy in predictability. but we gain in the knowledge that a large and diverse set of
compounds can be understood in terms of such simple parameters as relative sizes.
It may be noted in passing that although by far the largest amount of work on
crystal structures has been done in terms of the ordering of cations in a closest packed
structure of anions. this is not the only viewpoint. As is often the case in inorganic
chemistry, it is usually possible and often profitable to tum the model around 180". so
to speak. Thus interesting insights can be gained by considering the alternative:
placing the emphasis on the arrangements of cations.2
Fig. 7.5 Composite
struCture tielcl mup for
ABX. structures, X For
0 . !From Muller. 0 .: Roy.

R. Tltr Mqjor TtmDry
Structural
Sprinser- Vertaa: New
York, t974. Reproduced
with permission.!
tonic r3dlus (r1 ) in p m -
Muller, 0 .; Roy. R. 1M Major TRtltlrJ Slrtlctural FDmilirs;

New Yotk. 1974; PI'
76-78.
O'Kedfe. M.; Hyde, B. 0. In Strucwrr 11nd Bondlns In Crystals. O'Kedfe, M.; Navto&sl<y. A.,
Eds.: Acadcm;c: New Yotk. t911t; Vol. 1. w 221-254; Strm:t. Bundlns (Btrllnl 1935.6/, Tl.
I
258
7 Th Solid Stale
A Second look
a t the Transition
from Ionic to
Covalent Solid
In !he usual discussion of Fajans' rules as given in O!apter 4, emphasis is placed on

physical propenies such as melting points, solubility, etc. The possible effects of
covalency on struCture were also mentioned with regard to me fact that spl bolllling in
HgS could favor tile tetmhedral zinc sulfide structure (Oiapter 4). Therefore in
moving from an empirical structure field map to a semiempirical model (or semitheoretical, depending upon the viewpoint), we may take olhet' factors into account.
For example, we have previously seen that covalent character might be expected to
cause a switch from coordination number 6 to coordination number 4. Therefore, we
might attempt to bring in covalent corrections to improve a purdy mechanical or
radius ratio approach. There are two factors that increase covalency: (I) Small
differences in electroneaativity produce highly covalent bonds; (2) o ther tllings being
equal. smaller atoms form stronger covalent bonds than larger atoms (see Chapter 9).
To incorporate these two variables, Pearsonl has plotted the principal quantum
number. n (a rough indicator of size), versus a function of elecrroneptivity difference
(6x) and radius ratio. r. !r- and has shown that compoulllls with coordination
numw 4 segregate quite well from those with coordination number 6.
More recently, Shankar and Parr have designed structure stability diagrams in
which the compounds are plotted according to electronegativity and hardness (Fig.
7.6).5 When the data are presented in this way, the compounds segregate quite well by
structure and coordination number. The slope of any line passing through tile origin is
given by:
a 8 - u,.
m=--b,. + bu
(7.1)
This is the simplest expression for charge (ionicity) in the

system with
electronegativity equaliwtion (see Eq. 5.8S). The boundary lines in Fig. 7.6 radiate
mone or less from the origin with the slope of m from Eq. 7. 1. We may thus infer that
each represeru.s a line of constant ionicity that is responsible for tile changeover from
one structure type to the next.
Other workers have developed the ideas presented here to increased levels of
understanding." However. often increased precision is purchased at the expense of
simplicity.
compounds are usually considered 10 be covalently
Because
bonde<l. to a first appro:otimotion (see Chapter II). extended complex structures in the
soli\1 C:Jn ren<lily be related to them .
for example. rhodium pentaOuoride.
Obviously. it could be considered Ul5 an ionic structure. Rh5 sF-. und indeed the
crystal s trucmre7 consists, in part. of /Kp-arranged fluoride ions with modium in
octahedral holes. However. doser inspection of the structure reveals tha.t it consists
of tetrameric units, Rh.F:o, Ihat are distinct from one another (Fig. 7.7). The environment about each rhodium atom. an octahedron of six fluorine aJoms. is what we
W. B. J. l'h_.s. Or..m.
1!162 .2J. 103.
s,.;. U.S .A. 19&5. 81. 264-266.

' Hardness is a p-operty of an alOin or ion approximatdy inversely propor1ionallo ils pcUrWibilily. U
is
in acid-base discUSJions. See Chaper 9.
for discUS$iOns o(lhe prcdiCJion of1bc struCtures o( Mllids, starlins wi1h Ihe material prel<flletl hen:
and
far beyond. 5<e Bunlell. J. K. In
and 8cJmllfiJlln Cryswt.; O'Kec:ITc. M. K.:
Nuwotsky. A.. Eds.; Academic:
Yoric. 1981 ; Vol. I. Cho1per II; Adtl. Clwm. l'llys. lll!IZ. 49.
4
Shankar. S .: PllrT. R . 0 . l'rt><.', Null. Acad.
Motrd. B. K.; Zalkin. A.:
47.
A.; Bartleu. N. lnOfll. Chmt. 1973. 11. 2640-!644.
1.!
8-RC.<CI
e 6-6R<lCkS.I
0 -1 - -1 Wurmce und
Zinc: Bknd<
l.l
CN =6
1.0
LiX
Fig. 7.6 CryMnl ssrvclurcs C<MTdnled wish atomic chnrge (slope of linesl for lA-VIlA (1- 171.
IIA-VIA (2- 16). enJ"IIIA-VA (13-15) eompounds. The abscissa is lhc difference in
clcesroncgativisy. 6)( (liA and 1he ordin.we is lhe sum of charge coefficients (1) N !bl.
Note Jhutlhe clulrge. 6 '"" - llul/lbA + bnl. is approximaldy Jwice lhe TI!C'iPrtll'lll or the
slopes as plolled here.(Moditic<l from Shunlrur. S.: 1'-.lll'. R. G. Pruc. Nml. A<'ttu. Sci. U. S. A.
1985,82. 264-266. Reprotluce<l with permission. (
f'sg. 7.7 S1ercoview of die tetrameric unit of RhcF:o- The rhoclium Ill oms are a1 the CUllers
of lhe oclahedrn of fluorine a1oms. N01e bridging fluorine
(From Morrell, B. K. ;
Zalkin. A.; Tressau<l. A.; Bartll!t.l. N. Inorg. Chrm. 1973. 11.2640-2644. Reproduced wilh
permission.!
259
260
7 Tlo Solid Stole
should expect for a complex such as (RhF6 )-. Bridging halide ions are weU known in
coordination compounds. Furthermore, according to
rules, we should be
suspicious of an ionic structure containing a cation wllh a + S charge.
Sanderson& went so far as to say that even crystals such us alkali halides should be
considered as infinite coordination polymers with each cation surrounded by an
octahedral coordination sphere of six halide ions. which in tum bridge to five more
alkali metal atoms. Although Lhis point of view is probably of considerable use when
discussing transition metnl compounds. most chemists would not extend it to all ionic
lattices.
Laye red Structures
This brings us to a class of compounds too ol\en overlooked in the discussion of

simple ionic compounds: the transition metal halides. In geneml, these compounds
(except fluorides) crystallize in structures that are hard to reconcile wit h the structures
of simple ionic compounds seen previously (F"ogs. 4. 1-4.3). For example, consider the
cadmium iodide structure (Fig. 7 .8). It is true that the cadmium aloms occupy
octahedral holes in a hexagonal closest packed structure of iodine atoms, but in a
definite layered structure that can be described accurately only in terms of covalen t
bonding and infinite layer molecules.
Layered strucrures form, in some ways, an awkward bridge between simple
compounds with a high degree of ionicity (for which NaO seems always to be the
protocype), less ionic compOUnds with considerable covalency biJ( similar structure
(bot.h AgO and AgBr have the NaCI structure), and solids such as HgCI2 and
wherein the presence of discr-ete molecUles seems apparent. A scherrw.ic illustrating
the relationships among some of these structures in terms of size and eleclnric
structure might look like this:
lncn:asi111 pdarization due 10
dl:clron
and cation
declronoplivjty
lncrcuinc
potar;Uiion
due to
small calion
ond lut&e
onions
l:
Sio,
CdCiz
Cell,
HaCiz
Layered structures are e xtremely prevalcnl among lrnnsition metal halides. Examples
of compounds adopting the cadmium iodide slructure or the relaled cadmium chlo ride
structure (Fig. 7 .9) are:
M01 (M "' Ti, V)

MBr1 (M = Mg, Fe, Co, Cd)
Ml2 (M .. Mg, Ca. Ti. V, Mn , Fe. Co. Cd, Ge, Pb, Th)
M02 (M = Mg. Mn. Fe, Co, Ni. Zn, Cd)
MBr1 (M = Ni, Zn)
Ml 1 (M
Ni, Zn)
Sanderson. R. T. J. O..m. due. 1967,44, Sl6; l'olor Coo-ohnct; Ac.aderNc: New Yort. t9113; pp
16.S-17l.
The Structures of Complex Solids
261
Fig. 7.8 Stereoview of the

unit eel of the cadmium
iodide, Cdl,, struCture typc: ;
hc,..gOfl:ll, space group
1'3ml. Large circles, I;
smaR circles, Cd. !from
Ladd, M . F.
Stntt:IUU
c.
und Bondinr in Solid State

Eltis HWood:
Chi$ter. 1979.
Re.produc:ed with
permissicn.l
Fig. 7.9 Layered Slructure
of cadmium chloride,
CdC!,. Nole r ellllionship to
extended NaCI slructure
(missing atoms are dashed).
!From Welts. A. F.
StruclurDI lnlJI'fOnic
Slh cd.; Oxford

Unive.rsity: Oxford. 1984.
ReJlCoduccd with
permission.)
In the Cdl 2 structure. octahedral sites between eve.r y Olher pair of IJtp layers of
iodine atoms are occupied by cadmium atoms: C<IO! has cadmium in octahedral sites
between ccp layers. Actually, matters can get much more complicated than that:
There are tllru different Cdl 2 structures with varied loyers. To indicate the potential
complexity without going into the details ot the several possibilities,9 the structure of
one form of CdBrl wiU be memioned: It has a
repeating unit of halide
ions. ABCBCABABCAC, surely long-range order of a fairly high degree.
We have seen (Problem 4. I) that the change in stoichiometry from CsCI to CaF2
can be accommodated readily in the simple cubic system by merely "omilling" every
other metal ion; the resulting fluorite structure is highly symmetrical and quite stable.
This is not the case when covaleney becomes importanl. Fig. 7.9 illustrates this well :
Although the CdCI2 structure can be readily related to the NaCI structure. the
omission of alternare cations is not such as to leave a structure with the same high
symmetry: The 3-D cubic symmetry has been transformed into a 2-D layer symmetry.
For more neot1ycompletc dioawions see AclatM. D. M. '""l'llonic StJilds: wrrcy: New Yoot<. 1974:
pp 229-232; Wells. A. F. StructUI'all""'fanic Chtmistry, Slh cd.; Oxford Universlly: Oxford. 1984;
pp
262
7n Solid State
There is no simple explanation for lhe precise

of all of lhe layered
structures . But certainly the forces involved are complex. often subtle, and a hardsphere ionic model will not come close to accounting for them. As Adamslo has
pointed out:
" . . ionic theory is a good starting point for ge tting some gene.ral guidance on the
relative importance of factors s uch as size and coordina tion arrangement and is very
important in energetics, but for anything beyond this we must use the concepts and
language of modem valence theory and talk in terms of orbital overlap and band
structure. Ionic theory has had a good run .. (now about three-fourths of a century] ... it is still heavily overemphasited; so far as detailed considerations of crystal
s tructure are considered it is time it was interred."
These are the words of someone devoted to the details of solid state chemistry,
and they may be a bit overstated for the s tudent merely wishing a general knowledge
of inorganic solids, but they are weU taken, and certainly all of the interesting
subtle1ies of structure will be found to arise out or forces other than the electtostatics
of hard spheres. We shall examine these more closely later In this chapter.
Anothe r look at
Modelung Constants
It was noted in Chapeer 4 that the Madelung constant of a structure may be expressed
in various ways. The way that is concepually simplest in terms of the Born-Lande
equation is the simple geometric factor, A, such that when combined with the true
ionic charges, z> and z-, the correct eiCCITOSlatic energy is formulated. It
noted
that some wori<ers have favored using another constant, A. combined with the h ighest
common factor of
and
Z" .
Further ins i)1t into the stability of predominantly ionic compounds can be gained
by inspec1ion of the rtduc:td Mudtlung constanJ, A ' . 11 The reduced Madelung constant is closely related to the derivation of the Kapustinskii equation given earlier
(Chap ter 4). Templetonl l showed that if the laltice energy of a compound Mn.X.- is
formulated as:
(1 = 1.389 X I OJ kJ mol - 1 pml z+z- A'(m + xl
(7.2)
r.
2ro
then all Madelung constants reduce to a value ofllbout 1.7 (Table 7 .1). The usefulness
of this viewpoint is that it indicates tha1 despite the wide variety of ionic sizes.
compound formulations, and s tructures , there is basicaUy an upper limit to laltice
energy set by the constraints of geometry; ineffiCient struc tures may be somewhat
below it (though not far: There will a lways be an alternative s tructure near the limit)
and even effiCient s tructures may never rise above it.
1o Adams. D. M. lncwtlQnic: Solids; Wiley: New YO<it, 1974; p lOS. This is one oflhose
books 1hul
are inlereslin& 10 re:ld for pleasure as wdl as for inform111ian. A second QUOJe from Adams is:
PJosiurlse. plaJiarise. lei no one's wen escape: your eyes.' {Tom l..chmf' We ho .... obviously
fell 11181 bolh of Adams' Slalemenls are worth notina and followina!
11
ln pl:lce d lhe synilds A. A. A', some Jells (su Jolly, W. L Modrrn

C11mrurry;
McCraw-Hil: New Yoot. 198-4. and Ptfidd. W. M. lrt(>IJIOnic Clonnit"7: A Uni/inl ApfKoodt;
Addiscn-Wcsley: Readina, MA. 198-4) use M for lhe acometric factor, M for lhe can..enlional"
faaor, and M ' for the reduced fActor. The symbol -s by Tanplelon IS Footnole 12). who
inJtodllccd lhe concepl. WU Q,
12 TtmpleiOn. D. H. J. Clwm. l'lty. 1\155, lJ. 1826-11129.
Imperfections in Crystals
263
Table 7.1
A comparison
comfants
of Modelung
Co"'f'''o"MM,
M,X.
Geometric
Con-....rional
Reduced
factor, A
factor, A
factor, A
4.172"
25.031"
CaF2
2.Si9
S.039
2.244
2. 192
1.763
1.748
2.298
4.489
4.383
1.763
1.748
4.597
4.816"
1.641
1.638
1.68
1.68
I ..SO
1.46
1.76
1.75
Cdiz
csa
Naa
Si02c
2.408"
Tt02J
ZnS
ZnSf
1.641
1.638
1.47
1.60
1.64
1.64
Johnson, Q. C.; TCftll>)e&on, D. H. J. CNm. Phys. 1961, J4,
20!14.
" Exact values depend upon delails of otructure..

Crislobalitc.
J
R'utite.
' Wurtzite.
J iinc bknde.
Imperfections
in Crystals
To this point the discussion of crystals has implicitly assumed that the crystals were
perfect. Obviously, a perfect crystal will maximize the cation-anion interactions and
minimize the cation-<:ation and anion-anion repulsions. and this is the source of the
very strong driving force that causes gaseous sodium chloride, for example. to
condense to the solid phase. In undergoing this condensation, however. it suffers a
loss of entropy from the random gas to the highly ordered solid. This enthalpy-eruropy antagonism is
resolved in favor of the enthalpy because of the
uemendous crystal energies involved. but the entropy factor will always result in
equilibrium defects at all temperatures above absolute zero.
The simplest type of defect is called the Schottky or SchoUky-Wagner defect. It is
simply the absence of an atom or ion from a lauice site. In an ionic crystal, electrical
neutrality requires that the missing charge be balanced in some way. The
way
is for the missing cation. for example, to be balanced by another Schouky defea. a
missing anion, elsewhere (Fig. 7.10).
Alternatively. the missing ion can be balanced by the presence clan impurity ion
of higher charge. For example, if a crystal of silver chloride is "'doped" with a small
fig. 7.10 TINo Schonky

defects balancing each
other for no net charge.
Qo
a N
Absent Absc:nl
Na'
a
264
7 The Solid State
e e eG
G8
Fig. 7.11 Sdlouky detcc1

(cation vacancy) induced
and balanced by lhe
presen ol a hiaher
valence calion. (Hannay.
N. B. Solid-Srarr
Chrmisrry; Pn:nlice-Hall:
EncJewood Clift's. Nl . 1967.
Reproduced with
permission.!
amowtt of cadmium chloride, the Cdl+ ion fits easily into the sliver chloride lattice (cf.
ionic radii, Table 4.4). The dipositive charge necessitates a vacancy to balance the
in charge (Fig. 7. I 1). Closely related is the concept of"controlled valency," in
which a differently charged, stable cation is introduced into a compound oC a transition
metaL Because the latter has a variable oxidation state, balance is achieved by gain or
loss of electrons by the transilion metal. For eJWIIple, consider Fe. 7 . 12.
Stoichiometric nickel(ll) oxide, like aqueous solutions conaaining the Nil+ ion. is pale
green.
with a little
C3Ust$ a few ofthe'Cation sites to be occupied by + I
lithium in place of +2 nickel. This induces a few Nil + ions to lose electrons and
3
become Ni + ions. thus preserving the electrical neutrality of the CfYStal. The properties oC the NiO change drastically: The color chan&es to gray-black, and the former
insulator (to be expected of an ionic crystal. see 0\apter 4), is now a semiconductor. u
A rather similar effect can occur with the formation of nonstoichiometric compounds. For example, copper(!) S\JIIide may not have the exact ratio of2: 1 expected
from the formula, Cu1 S . Some of the cu ions may be absent if they are compensated
by an eq\Jivalent number ofCu1 ions. Since both
and Cuh ions are stable, it
eu
eeeee
0@080
Fig. 7.12 Conlrollcd

valency tNi10 ..... Ni') by
addi1ion of Li ions 10
NiO. (from Hannay. N. B.
Solld-Sialr Chrmisrry;
PrcnllceHall: Enalewood
Oift's. NJ. 1967.
Reproduced wilh
permission. I
eeeee
!"'perfections in Crystals
265
eu.., .
is possible to obtain stoichiometries ranging from the ideal to

If the "vacancy"
is not a true vacancy but contains a trapped electron at that site, the imperfection is
called an F center. Fo r example, if a small amount of sodium metal is doped into a
sodiwn chloride crystal, the crystal energy causes the sodium to ionize to Na + + eand the electron occupies a site that would otherwise be filled by D chloride ion (F'J8.
7. 13). The resulting trapped electron can absorb li&:ht in the visible region and lhe
compound is colored (F "' Ger. Farbe, color). The material may be considered a
nonstoichiometri<: compound, Na 1..aCI. or as a dilute solulion of "sodium
eleclride. "15
If the missing ion has not been completely removed as in a Schottky defect. but
interstitial site, the result is called a Frenkel defect (Fig.
only dislocated to a
7 . 14). The vacancy and
inrerstitial ion may be caused by a cation or an
anion, but because the cation is gene111Uy smaller than the anion, it will usuaUy be
easier to fit a cation into un interstitial hole olher than the one in which it belongs. For
the same reason, although it is theoretically possible to have both interstitial C3lions
and anions at the same time, at least one wiU ordinarily be energetically unfavOOlble
because of
size.
F'og. 7.13 An F ceneer. an

e1ec1 ron occupyq 1111
anionic aile.
Qo
cr
Na'
Fig. 7.14 A Frenkel defecl:

a calion displaced (rom its
normal site.
Qo
........, C.oion
Where B is snoll wilh rcspecllo 1.

"See 0...,aet 10 for solucions or sodA.m dcclri<le in liq!Ad atMIOnia..
"Fine. M. E. In Tuadn<HO SolidSIDkCiwml.slry. Voi. I: Th' C1o'mi<G1Strucwuof$oll4s;Hwr.y.

N. 8 ., Ed.; Plall.lm: New YO<I<. 1973; pp 217-290.
266
7 The Solid Stote
Conductivity
in Ionic Solids
Conductivity b y
lon Mig rotion 17
Normally, ionic solids have very low conducrivlties. An ordinary crystal like sodium
chloride must conduct by ion conduction since it does not have penially filled bands
(metals) or accessible bands (semiconductors) for electronic conduction. The conductivities that do obtain usually relate to lhe defects discussed in the previous section.
The migration of ions may be classified into lhree types.
1. Vacancy mechanism.
If there is a vacancy In a lattice, It may be possible for
an alljacent ion ofthe type that is missing, normally a cation. to migrate into it,
the diffiCulty of migration being related to the sizes of the migrating ion and the
ions that surround it and tend to impede it.
2. Interstitial mechanism. As we have seen with regard 10 Frenkel defeCis, if an

ion is small enough (again, usualy a cation), it can occupy an interstitial site,
such as a tetrahedral hole in an octahedral lattice. It may then move to other
interstitial sites.
3. l nterstitialey mt>cluJnism. This mechanism is a combination of the two
above. It is a concerted mechanism, with one ion moving into an interstitial site
and another ion moving into the vacancy thus created. These three mechanisms are shown in F'rg_ 1- IS_
In purely ionic compounds, the conductivity fro m these mechanisms is intrinsic
and relates only to the entropy.(jriven Boltzmann distribution ; the conductivity will
thus increase with increase in temperature. Because the number of defects is quite
limited, the conductivities are low. of lhe order of 10- 6
em-. In addition.
extrinsic vacancies will be induced by ions of different churge (see page 264). There
exis t, however. a rew ionic compounds that as solids have conductivities several
orders of magnirude higher. One of the first to be studied and the one with the highest
em- , is rubidium silver iodide, RbAg.ls.
room-temperarure conductivity, 0.27
n-
n-
- - ltlceru.tbJ
- --
lnl<nlitwcy
Fig. 7.15 Mechanisms or ionic conduclion in crystals wilh lle(ea struc:lui"C3: (a) vacancy
(Schonky defccJ) mechanism. (b) inlenlilial (Frtnkd daect) mcch:lnism. (c) inrcrstiriak:y
(concerted Schouky-Frcnkcl) mechanism.
Fanirl!lon. G. C.; Briani. J . L

tm, .l!Of. 1371. Ww . A. ft.
Wiley: New Yod. 1988: pp 300-llG.
,. Geller, S. Ace. Chffl!.
In&. II. 81. See olso FOOIIIOIC 17.
17
Conductivity ;., Ionic Solids
267
The ronduclivity may be compared with that of a 35% aqueous solution of sulfuric
ocid, 0.8
e m - . The slrucJUre ronststs
romplex (not a simple closest-packed)
arrangement of iodide ions with Rb Ions in octahedrul holes a nd Ag ions in
tetrahedral ho les. Of the 56 tetrahedral sites available to the Ag+ ions. only 16 are
oc.c upied . leaving many vacancies . The rela tively small size of the silver ion ( 114 pml
compared with the rubidium ( 166 pm) and iodide (206 pm) ions give the silve r ion more
mobility in the relatively rigid latice I)( the Iaue r ions. Furthe rmore. lhe vacant sites
are arranged in channels. down which the Ag can readily move (Fig . 7. 16).
Another solid electrolyte thru may lead 10 important practical a pplications is
sodium beta alumina. Its unusual name comes from a misidentification and an u ncer-
n-
Fig. 7.16 StrucJure d RbAg.l, a-yslol. Iodide oons arc

by large spheres.
rubidium ions by sm:dl while spheres. Telr:.hcdral
>llllable for ilvcr ions are marked
with shof1 skevcs on horizomal
(The easiest to see is perhaps the one formed by the
iodide ions fnonl lefl with I he fourth iodide ion behtnd and to lhe ri&)ll.)
Conduction is by movement of Aa ions from one te.l r:>hedl'lll site 10 the
down channds
or
in the crystal. One channel may be -Jl curving downward from upper center 10 loWer leO
(inctudina the site mentioned above). (From Geller, S.
t967. /$7, 310. Reproduced
with permission.}
268
7 Tlle Solid Stole
tain compo5ilion. It was first thousJ!t to be "P.alumina: a polymorph o f lbe common

y-alumina. Al2 0 1 Its actual composition is close to lbe stoichiometric
(- NazO II A12 QV, but lbere Is always an excess of sodium, as, for example,
Naz.saA1 2 uOw 'The strucrure is closely related to spinel. with SO of lbe S8 atoms in
lbe unit cell arranged in exactly the same position as in the spinel structure.19ln fact,
sodium beta alumina may be thought of as infinite sandwiches composed of
of
spinel strucrure with a filling of sodium ions. It is the presence of the sodium between
the spinel-like layers that provides the high conductivity of sodium beta alumina. 'The
AI-0-AIIinkages between layers act like pillars in a parking carage (Fig. 7. 17) and
keep lbe layers far enough apart thnt the sodium ions can move readily, yielding
conductivities as high as 0.030 n-cm - . There Is a rela ted structu re caUed sodium /3"
alumina with the layers held farther apart and with even highe r conductivities of up to
O.lsn- em-
The re are many porenlial uses for solid electrolytes, but perhaps the most attractive is in batteries. Recall that a battery consists of two very reactive substances (the
more so, the better), one a reducing agent and one an oxidizing agent (see Olapter 10
for a discussion of inotganjc electrochemistry). To prevent them from reacting directly, these reactants must be separated by a substance that is unreactive towards
both. and which is an electrolytic conductor but an electronic in.sulutor. Generally (as
in the lead storage battery. the dry ceU, and the nickel alkaline battery), solutions of
electrolytes in water serve the last purpose, but in most common batteries this reduces
the weight effeciency of the battery at the expense of reactants. The attractiveness of
solid electrolytes is that they might provide more efficient batteries.
Fig. 7.17 Relation of the spinel Slruelure (lel'l) to the structure of sodium beta alumina
The sndium ions are free to move in the open spaces between spinel blocb. held
apart by At-o-AJ pitlan in the "partcina Ptlle" saructurc. (In part from Wells, A. F.
Structural Inorganic Clwmisrry, Slh ed.; Oldani UniYC!Uy:
1984. Rq,roduced with
permission. I
"Wells, A. F. Srruclllal ln<Ntttic
Sth cd. ; Cluerdon: Odon:l, 1984: pp S98-S99.
Solids Held Together by Coval- Bonding
269
JS
Na
Molten tedium
declt'Oclc
Molb:tl ufur
declrodc:
Soclrum beta oluoftna

2No+JS
2t sl-
f"og. 7.18 Sodium/SUW.r baltcry with a sodium beta alumina sdid electrolyll!.
Consider the battery in Fig. 7. 18. The sodium bela a lumina barrier allows sodium
ions formed al the anode to flow across to lbe sulfur compartment, where, toaethcr
with the reduction pr-oducts of Ihe s ulfur. il forms a solution of sodium trisullide in the
sulfur. The latter is held at 300 c lo keep it molten. The sOdium beta alumina also acts
like an electronic insulalor to prevent s bon circuits. and it is inert toward both sodium
and sulfur. The reaction is reversible. At the presem state of development. when
compared wilh lead storage cells, ba n eries of this son develop twice the power on a
volume basis or four times lhe power on a weight basis.
Solids Held Together

by Covalent Bonding
Types of Solids
Because some of the pr-operties of solids lbal contain no ionic bonds may be convenienlly compared with those of ionic solids. it is u sefu llo inclUde them here despite
the faCl that Ibis chapter deals primarily with ionic compounds.
We may classify solids broadly into three lypes based on their electrical conductivity.
Metals conduct electricity very well. In contrast . insulators do not. Insulators may
consist of discrete smaU molecules, such as phosphorus triiodide, in wbic.b the energy
necessary to ionize an eleCiron from one molecule and transfer It to a second is too
great to be effected under ordinary potentials.lO We have seen that most ionic solids
are nonconductors. F"maUy, solids that contain infinite covalent bonding such as
diarnooo and quartz are usually good insulators (but sec Problem 7 .S).
The third type of solid comprises the group known as semiconductors. These arc
either elements on the borderline between metals a oo nonmetals, such as silicon and
270
7 The Solid State
germanium, compounds between these dements, such as gallium arsenide, or various

nonstoichiomelric or defect structures. In electrical pr-operties they fall between
conductors and nonconductors (insulators).
Bond Theory
In order to understand the bonding and pr-operties of an infinite array of atoms of a

metallic element in a crystal, we should first examine what happens when a small
number of metal atoms interact. For simpliciry we shall examine the lithium atom,
since it has but a single valence electron, 2s1 , but the principles may be extended to
transition and posttransition metals as well. When two wave functions interact, one of
the resultant wave functions is raised in energy and one is lowered. This is discussed
for the hydrogen molecule in Chapter 5. Similarly, interaction between two 2s orbitals
of two lithium atoms would provide the bonding a energy level and the antibonding a*
energy level shown in Fig. 7.19. Interaction of n lithium atoms will result inn energy
levels, some bonding and some antibonding (Fig. 7.20). A mole of lithium metal will
provide an Avogadro's number (N) of closely spaced energy levels (the aggregate is
termed a band), lhe more stable of which are bonding and the less stable. antibonding.ll Since each lithium atom has one electron and the number of energy levels is
equal to the number of lithium atoms, half of the energy levels will be filled whether
there are t wo, a dozen, or N lithium atoms. Thus, in the metal the band will be half
filled (rig. 7.21), with the most stable half of the ene.r gy levels doubly occupied and the
least stable, upper half empty. The preceding statement is true only for absolute zero.
At all real temperotures the Boltzmann distribution22 together with the closely spaced
energy levels in the band will ensure a large number of half-filled energy levels. and so
,..-------o
\
'>u2.s
\
___
,..__
Fig. 7.19 lmenaion of the 2s om.lals oflwa lilhium aloms to form a and u molecular
ot1li1als.
cr. F'IJS. 5.1. 5.7.
11 The levels ncar Ihe ccnler of lhe band ase essentially noobondina.
Z2 In the Bollzmam distribution, lhe populalion ofhisl>er netJY stales wil be relaled to the value of
lhe oxpn:ssion r""" wl1ere ' is lhe base of nawral lopri1hms, is lhe eneray of the hiahco" Slate,
k is BoiiZllWWl's tooslanJ, and Tis I he eb&olute lempetalure.
Solida Held Together br Covolent Bonding
271
or
Fig. 7.20 lmeraclion or eight 2s orbitals eight lilhium atoms. n.e spacing or the energy
levels depends upon the geometry of the cluster.
or
fig. 7.21 Bonding or a mole lithium atom 2s orbitals to form a half-filled band. Heavy
shading Indicates the filled portion
the band. the IOJ> which is caled the Fermi level, .,..
The real Situation is somewhat more complicated because the 2p orbitals can internet as well.
or
or
the sharp cutoff shown in Fig. 7.21 should actually be somewhat fuuy. The top of the
filled energy levels is termed the Fermi level (Ep).
Each energy state has associated with it a wave momentum either to the left or to
the right. If there is no polential on the system, the number of states with electrons
moving left is exactly equal to the number with electrons moving right, so that there is
no net flow of current (Fig. 7.22a). However, if an electrostalic potential is applied to
the metal, the potential energy of the states with the electrons moving toward the
positive charge is lower than the slates with them moving toward the negative charge;
thus, the occupancy of the states is no longer SO:SO (Fig. 7.22b). The occupancy of
states wiD change until the energies of the highest left and right states are equal. Thus,
there is a net transfer of electrons into states moving toward the positive charge, and
272
7 n.. Solid State
(a)
.,
'
Ekctron rN)'ItmcnJ ten
Elc<lton mo..ment rilht
rais<d ;.. "'<'ll'
Jowcml In <nam'
(b)
Fig. 7.22
an electric: lidcJ on the entra:Y levels in a mew: (a) no lidcl, no net llow
of electrons; (b) field app!M:d, net llow of dcclrons 10 the right.
the melal is conducting electricity. If the band is completely filled (Fig. 7.23). there is
no possibility of transfer of electrons and, despite the presence of a potential, equal
numbers of electrons flow either way; therefore, the net current is zero and the
material is an insulator.
Intrinsic and
Photoexcited
Semiconductors
All insulators will have a filled valence band plus a number of completely empty bands
at higher energies, which arise from the higher-enercy atomic orbitals. For example,
the silicon atom will have core electrons in essentially atomic orbitals ls2, 2s2, and
2p6, and a valence band composed of the Js and )porbitals. Then there will be empty
orbitals arising out of combinations of Jd, 4s, 4p . and higher atomic orbitals. If the
temperature is suffiCiently high, some electrons will be excited thermally from the
valence band to the lowest-lying empty band, termed the conduction band (Fig. 7.24).
The number excited will be determined by the Boltzmann distribution as a function of
temperature and band gap, f.. Before
the source of the f118811itude of the
e.nergy gap, let us note typical band-gap a nd conductivity values for insulators (diamond, C), semiconductors (Si, Ge), and an "almost metal," aray tin. 21
Bandpp, kJ mol- 1
Conductivity, n-
=-
11
s..
Si
Ge
.S80
105
69
< 10- 11
s )( to-
0.02
lgroy}
1
104
Van Vlack. L H. Ekmrnrs cf Mourlols Sdeftct and EntfnMI. Slh cd. : Addison-Wesley:
MA. t98S; p 303. Gny lin lw lhc SM>t Sli\ICIIn as diemoftd. Metallie lin is alcd while
lin and 1w a distoncd oc:hl1cdral environment about each lin lltom. It conduds dcclric:ily like other
me181s.
Solids Helcl Together br Covalent landing
273
Fig. 7.23 Effect of an

electric tidd on an
insulolor. Even with apPlied
pOtential, flow is equal in
boch directions.
excilation of electrons in .,..

intrinsic semiconductor.
Tlle x's represen1 eleclrons
and 1he o's holes.
..
For every electron excited to the antibonding conduction band, tbere will remain
beflind a hole, o r vacancy. in tile valence bond. The electrons in both the valence band
and the conduction band wiU be free to move under a potential by 1he process sllown
in Fig. 7.22b, but since the number of electrons (conduction band) and holes (valence
band) is limited, only a limited shift in occupancy from left-bound srotes to right-bound
states can occur and the conductivity is not high as in a metal. This phenomenon,
known as intrinsic semiconduclion. is the basis of thermistors (temperatu re-sensitive
resistors).
An alternative picture of the conductivity of the electrons and holes in intrinsic
as
semiconductors is to consider the electrons In the conduction band as
expected, toward the positive potential, and to consider the holes as discrete. positive
charges migrating in the opposite direction . Although electtons are responsible for
conduction in both cases, the hole formalism represents a convenient physical picture.
If, instead of thermal excitation, a photon of light excites an electron from the
valence band to the conduction band, the $all'le situation of electron and hole carriers
obtains, and one observes the phenomenon of photoconductivity, useful in photocells
and similar devices.
274
7 The Solid Stole
Instead of silicon or germanium with four valence electrons (to yield a filled band
of 4 + 4 = 8 electrons on band formation). we can form a compound from gallium
(three valence electrons) and arsenic (five valence electrons) to yield gal lium arsenide
with a filled valence band. In general, however the tJ.Efor the band gap will differ from
those of elemental semiconductors. 'The band gap wiD increase as the tendency for
electrons to become more and more localized on atoms increases, and thus it is a
function of the electronegativities of the constituents (fig. 7.25). Note that conductivity is a continuous property ranging from metallic conductance (Sn) through elemental semiconductors (Ge. Si). compound semiconductors tGaAs. CdS) to insulators. both elemental (diamond, C) and compounds (NaCI).
Impurity and Defect

Semiconductors
Consider a pure CrYStal of germanium. Like silicon it will have a low intrinsic
conductivit y at low temperatures. If we now dope some gallium atoms into this
CrYStal, we shall have formed holes because each gallium atom contributes only three
electrons rather than the requisite four to liU the band. These holes can conduct
electricity by the process discussed above. By controUing the amount of gallium
we can control the number of carriers.
Thinking only in terms of electrons or holes that are completely free to move
suggests that there would be no energy gap in a gallium-<loped germanium semicon-
Noel
700
600
:::- soo
'lS
E
II.
,!JOO
200
100
ooxA -
17.$ltn oox. - a1.s1tn
Fig. 7.25 Empirical relalionsllip between eneray Ia!' and lhe dectronepaivilies o( the
ekmenls present. Note lllat substances made from a sins)e, fairly de<:tronqaJive atom
(C. diamond) cw from a very low-dcctronq.alivity metal and hiah<lcctronesaliMy nonmetal
(NaCIJ are sooc1 insulators. As the electroneptivities approKJ11.7S. lhe de<:troneptivity
functioft np;dly
uro.(From Hanney, N. B.
Prentice-Hall:
En&)ewood Cljfs. NJ, t967. ReprodUced with petmlssion.l
Solids Held Togethow by CoYolent Bonding
275
ductor. However, note that gallium lies to the left of germanium in me periodic table
and is more electropositive; it thus tends to keep the positive hole. (Alternatively,
germanium is more electronegative, and the electrons tend to stay on the germanium
atoms rather than flow into the hole on the gallium atom .) This electronegativity effect
creates an energy gap, as shown more graphically in Fig. 7.26. The electronic energy
levels for gallium lie above the corresponding ones for germanium24 and thus above
the germanium valence band. Providing a small ionization energy, ll.E, generales the
holes for semiconduction. The resulting system is caUcd an acceptor (since gallium
can accept an electron) or p-type (p - positive holes) semiconductor.
In an exactly analogous but opposite manner, doping germanium with arsenic
(five valence electrons) results in an excess of electrons and a donor (the arsenic
donates the fifth electron) or nlypc: (n negative electrons) semiconductor. The
conduction can be viewed in terms of an energy diagram in which the electrons can be
removed from the impUrity arsenic atoms to the conduction band of the semiconductor
7.21).
J;g. 7.26 Conduction by
holes in an acceptor or
p-lype temic:onduc:t.
Fig. 7.V Conduction by

electrons in a donor or
nlype semiconductor.
276
7 The Solid State
Various imperfections can lead to semiconductivity in analogous ways . For

example, nickel (II) oxide may be doped by lithium oxide (see Fig. 7. 12). The N;;l+ ions
now behave as holes as they are reduced and produce new N;l+ ions at adjacent sites.
These holes can migrate under a potential (indicated by the signs on the extremes of
the series of nickel ions):
(+JN2+ .. N1 . ... . N1 . ... Ni1 + Nil+( - )
The r311ge of possibilities fOf'

is very great, and lhe applications to the
opcr:llion of transistOfS and relaled devices have revolutionized the electronics industry, but an extensive discussion of lhese topics is beyond the scope of this text.l.S
Note, however. that inorganic COI11l<lUflds are receiving intensive attention as the
source of semiconductors, SIJ9CTCOnduc!OfS (PQge 28S), and one-dimensional conduc
tors (Chapter 16).
Solid-State
Materials with
Pola r Bonds
We have seen basically two models for bonding in sevenl types of solids. The ionic
model (Chapter 4) has comple.t e localiUllion of electrons on the ions, patently untrue
but a useful approximation in crystals
very electropositive metals and very
electronegative nonmetals. A completely covalent insulating solid such as diamond is
basically the same: All of the electrons are localized in C- C bonds. The band model
for conductors (above) has lhe valence electrons completely and evenly delocalized
over the whole crystal. Semiconductors fall betweeen insulators and conductOfS in
that the elect rons are localized but with a small energy gap. Most solid compounds will
not fall nearly into any of these simple pictures, just as most molecules are neither
completely covaleat nor ionic. The current picture for bonding in many interesting
materials is a composite of these two extremes. It wiU be illustrated by an examination
of compounds belonging IO the
structure type.
See JoDy. W. L Mt>tkrn lnnrganlc Chtmlltry; McCnw-HiH: New Yo.tc, 19114: Wesl. A. R. BDSic
Solid Slou Chtmlstry. Wiley. New Yo.tc. 1988: I'P 294-300.
""See Holfmann. R. Solld.sond Swfocn; VCH: New Yo.tc. t9a&. forac:leardi.scussionol'solid swe
chemis.l,y and physics in
larcuaae for lhis stcueturc as well as m8fty oChers. This
dUalssion may also be found ito Hotrmann, R. ilngtw. Clwm. 1m. 26, 846-811;
Mod. l'loys.
1!188. 6Q, 60t-Q8. The op<cific: cUinllk for ll1is seaion is clucribed In an artide wilh lhe same lille
as lhe headinJ above; see
:M.
Solid-State Materiab with Polar Iondo
The ThCr2Si2
Structure Type26
277
More !han 400 compounds d AB:X2 stoichiometry adopt the

type structure.27 In these A is typically an alkali, alkaline earth, or rare earth metal. B rn:IY be a
transition metal ora main-group metal. X is a group VA (IS) , IVA (14), or occasionally
IliA ( 13) nonmetal. The compounds in which we shall be most interested are composed of an alkaline earth metal (A = Ca, Sr. Ba), a transition metal (8 - Mn. Fe. Co.
Ni, Cu), and phosPhorus (see Tllble 7.2). These compounds are isostruclural and
crystallize in the ThCrzSi2 strucrure with space group 14/mmm. The unit cell (Fig.
7.28) consists of eight A11 ions at the corners of a rectangular parallelepiped plus one
Table 7.2
Some ;..tOfllfomic di..ancn in
Compaomd
CiFe:Pl
CaC'.ozP,
CaNi:tP1
'x-P
a
c.-r
l04
299
300
lOS
302
:!:3
compcunds wilh the
,._,
Compound
224
226
l7l
245
.n<J
238
230
22S
:!:6
243
21
21!1"
Srf'e,P2
ScCo,P2
SrCut_."P1
stnlchl...
,._, ,._,
no
318
3t6
318
22.S
22.4
343
243
231'
II
2JO
}42
Campao;nd
,.._,
BaFezP2
3-41
332
30S
336
61
:t6
"--r
24S
226
373
384
236'
378
8
13
Dlla from Mewit, A. Z. NDIIll'/tnch. lliiO, JSB, 141- 14S. All diSianc:es in pm.
Thi1 compound contain bolh Cu" and Cu"'
StalllllcaRy me4ninatess Iince r8 varies do\on the series.
Fig. 7.28 Unit cd olan

alklliJ>e eanh (AI/
transition metal (8)/
phosphide (I')
or lhe
ThCr:Si2-typc: stf\ldure.
T
,,_,
The distances listed in

Table 7.2 are
(Modifterl
BtCri
P!SiJ
rrom Hoffmann.
R. ; Zhcna. C. J. Plf:;s.
1985.119. 417.S--tl81.
Reproduced with
permission.)
n In CS)'$1aD..,...,y, u in systcmaJic bolany and Z<><*>IY the

is mcnly a "namebeam-"SCli11Cthinato which a name may be ouached unnmbiauously. h is not ncccsurily the 1ypicol spec:'oes
in rhe
mcanina of thut word ( m representaJive, usual). Althou&h this can cewe scxne
initial corluaion, nolc thai the ovcnll sloiclliomctry and the tolol number of sand p electrons (u
pvcn by the Roman l1tlllltnlan>up numbusl are Jhe same in bolh
and
278
7 Tloe Solid State
body-centered A11 ion . The

metal atoms ( 8 11) and the phosphorus atoms
occur in
layers, each in a square array such that each metal atom
surrounded by a tetrahedron of phosphorus "liaands":
O B
Note the capping phosphorus atom atop the sqUllfe pyramid: It is coordinated to four
metal atoms. all on one side, highly unusual for an ion. However. if we ask whether
this is an extraordinary covalent structure for a nonmetal, we note that it is not at all
unusual for sulfur (cf.
Fig. 6 .4).28 Althoullh cllfTetltly unknown for phosphorus in
a simple molecule, a similar strUCture would be expected for the isoelectronic :PF;
anion if it existed.l9
If we examine the distances list ed in Table 7.2 some interesting facts emerge. For
a given metal A. the A-Pdistance is constant as we might expect for an ionic alkaline
earth metal-phosphide bond. Funherrnore. these distances increase calcium < strontium < barium in increments
about I S pm as llo the ionic radii of
and
Ba2 (Table 4.4). However. the B-P distances vary somewhat more with no periodic
trends (Mn. Cu larger; Ni. Fe, Co smaller). Most interesting. however. is the larger
variability in the P-P distance from about 380 prn (Mn, Fe) to 2:!5 pm (Cu). As it
turns out, the lower limit of 22S pm (Cui is a typical vulue for a P- P bond (Table E. I,
Appendix E) and 380 pm is approximately twice the van der Waals radius of phosphorus.JO Funherrnore, there is a sleady reduction this distance as one progresses
across the transition series. All of this is consistent with the hypothe!>is that this is an
electronic (covalent} effect.
Before examining these electronic effects. we should delve u liule more lleeply
into the theory and terminology
solid stole chemistry than was done on pages
269-272. Specifically. if there is on infinite army of illcmi<:ol
Is (say H b )
represented by t/>0 "'
<f,1 related by translational symmetry :ond spaced at
distance u. then we can have linear
1/J,:>t
or
ea:. sr.
or
or
,. II mi&)lt be objected thai the fouc bonds in " triaonul bipyr.unidal" SF cnnsisl of two short
equatorial bonds and 1wo lofllcr ui:ll bonlb. Rec:lll
lhe very slillhl dill'crencc in cnusy
be1ween the TBP s1ruc:hre :ln4 1he squ:ll'e
In a rtcl:l"PPIM lauice. the l:lucr
will be favoured.
anion ul HPF4 acti111 as a
'"Thi. woolcl be the
acid. The che..U.ry ot 1he
1\oorophosphonn is not ..a! known. bul ohe correspondina

lq.. CH,PF.l an
wdl known and have Slruclures similar to the one ...uestcd (see Chapter 6).
liO Covalent
t*liiiiiiCI wnob' Waals radii lrolve not yet beendis<:usscd in any dclail (see
bul
should be familiar with the acneral
from previous c::ounes.
Jl Sec I he ciscussion ofU:AQ.MOihcory. 0...1er j(Eqs. 5.26. 5.27) ..tlen fclialomie molec:ub,
the
...
.... a
..,
and ....
Solid-State Materials with Polar Bonds
279
1-o-1
n = 0
4>)
4 .. .
4>.
(7.3)
"'k =
where 4>,. is the basis function of the nth orbital. i = v=l, and e is the base of natural
are called Bloch functions and k is an index
logarithms. The linear combinations.
that indicates which combination (irreducible representation) is involved. To return to
the previous discussion of the analogy between band structure and a mole of molecular orbitals. consider two v-d!ues fork.
"'k
l fk = 0:
(7.4)
-o-o-o--o-o--
(7.5)
From simple MO theory, we expect that this nodeless function will be the most
bonding state.32 It thus represents the bottom of the band.
-o-o-o--o-o--
(7.6)
(7.7)
This is the most antibonding state. These t wo define the bOitom and the top of the
band. The situation is the same as we have seen previously for lithium. whether there
are two, eight. or a mole of hydrogen atoms in metallic polyhydrogen.ll Now what we
>!
llhou!d not be
k
!owesl5181e. !flhe basis funclionare p,
(where: the trnnslalionat ymmctry
along the axi.<l. 1111 witt have the nrrw nodes and be
highc.t in energy;.;.,. wilt hove no nodes and be ro_,.t in energy. See Foolnote 26.
A1>01her UIT:IY of orbitoh< with the same sort of linear combinalions il< lh:U of lhe " syslem of
eyc!opolyencs !benzene. Mphthalene) wirh wflic:h you are probably already Cam;tiar. The molecular
orbital.s consttucled from sets ol P""'tlc! p orbila!s are both
and :mlibonding"' various
energia. lbe syxtem is panicularly<lableifHilcke!'s rule (2tr + 2eleetron: see also Cbac>ler lSI is
1
obeyed. In lhe .,_ of:m infinite array ofhyliqen utoms ( !s ) . 1he sicu:uion is unscoble las you
shoukl have questioned immediale!y); it revtfls to on
ol H2 molecules;
H
H H
H H - - H-H
H-H H-H
This is wfly lithium was chosen ns an examc>le in

discussion: PotyhydtCJ8cn is unstoble lll
ordinary pr...ures. Now what lhe chcn-.1 taJces as intuitive. the solid <tale phy<icis1 calls a
"Peiet1' distonion.'' In the case ollit!Wm. a solid results becau# oft he mixing of andporbitals.
lbere are many Olher intercsli"8 and important (and certain to become more so) processes hiding
under different names and different viewpoinls in solid state chemistry nnd physics, but they are
beyond the scope of this book. The interesled reader is referred to Fool note 26. Whether hydrn
becomes melaOic: at auaine.ble. hish pru$1JIU is slil a mull ol some uncertainty. Mao. H. K.:
Hemley, R. J. Scimcl! tm. 144. 14<>2; 1990.247. 863-U4. Silvera, I. F. ll>id. 1990, 247, 863.
280
7 ne Solid State
have drawn previously as a block to represent the aggregation of a very large number
of orbitals (cf. Figs. 7. 19-7.21 with rhe simplified diagrams here):
..
...
..
.
.....---
''
-.....
the physicist plots as an enersy function:
--0---rO--
I
I
I
I
IElc:.
I
J:
a/o
This graph conveys the same importnnt information given by the energy level <.liagram:
The number of states (molecular Ol'bitalsl generated by the linear combination of
atomic orbitals in Eq. 7.3 is 110( evenly distributed over the energy range. but is
densest at the bottom and top. The number of s tates in the interval E + dE is known as
the den.sity of
(DOS):
As can be readily seen. the density of Slates at any given eno:rsy is invern:ly proportional to the slope of the enersy fUnction Ill that ener&y.
The density of slates for this type of system may be worked out qualitatively
rather easily.M We shall make some simplifications. First, we shall assume that in the
compound
the barium ocaJrs as simple cations having no covalent interac-
>'For lhe C0ft1'1Cie disaos1ioto, see Holfmam. R. ;
2Jiuls, C. J. l'lrp. Clwm. ltl5. 119. 4175-4tit .
Solid-Stole Materials with Polor Bonds
281
lions with lhe remaining atoms.lS Then we shall let the phosphorus atoms interact with
the metal atoms as thougJI we were dealing wilh a discrete, tetrahedral, molecular
complex of the sort
.l6Jn such a situation. molecular orbital theory gives
a set of four bonding MOs (a 1 + t:l which come from the atomic 4.s and 4p Ofbisals of
lhe metal and lhe phosphorus lone pair orbitals of the same symmetry:
4p
:=
....;nJymmld
=
M
The orbitals which are principally nonbonding metal 3d in character nre split inlo an e
set and a t2 se . The latter splitting will be discussed at some length in Chapter II and
need not concern us too much at present. Finally,there are the
orbitals.
a; and r; amibonding
Correspondingly. we can calculate the band structure and density of states for lhe
extended Mn2Pi- layer (Fig. 7.29). We have seen previously (Chapter 5) that if the
interacting AOs are distinctly separate in energy. we can treat the resulting MOs as
tllouBh they came essentially from only lhe AOs of a given energy. We thus can look at
lhe DOS for lhe extended Mn2 Pi- layer and find the origin of the bands. The lowest
( -19 eV) corresponds to the o 1 orbital of the isolated complex and comes from the
manganese 4s orbital and the phosphorus Js orbitals. The next ( - 1.5 e V) correspOnds
to mang;.tnese 4p and phosphorus Jp. It is possible to decompose these bands into the
relative contribution of manganese and phosphorus (Fig. 7 .30) and. as we should
expect from the lower electroneg;.tlivily of manganese. these bands are dominated by
the phosphorus. In contrast to these two bands which are mostly phosphorus but
partly manganese, at higher energies (between - 13 and -8 eV) we find that the
electron density is almost entirely on the manganese. In isolated metal complexes
these are the approximately nonbonding metal d orbitals.
n This turns out to be ""oversimc>Uficelion: we have '<en thatth<rc is no such thina as a perfectly
ionic bond, but the simplification docs not cau<c serious errors (sec Footn<Xe 34).
l6 Discrete tcJrohedi'BIIMn(PR,I.P c:omplexes have apparently nol been p<cp:u-cd, but MntPR,),Iz
wilh
c:onsisls of distorted lctrnhcdral molecule$. /u we sh:lll see (Chap>er Ill pi>Mphill(:
la"ic positive charles on the transition metal will be less stable than wllen there is mote eleclron
density on the meul, as in the [B2 Pzl1- layer. The present MO discussion :mel 111< MO diaanm
anticipate the Wcuuion of molecular orbital theory in complex"'l in Chapter II and may
most prditably be read aa;Un aneo- readins thai c:hapler.
282
7 The Solid Stote
Separate lloms
Mn-P bonding
lllrned on
Exlended imeractions. _23 .....__ _ _:---'------'L--- ---..,.----...J
especially Mn . .. Mn
bonding, turned on
DOS
lc -
Fig. 7.29 Left: Energy levels of separaled Mn and P atoms. Mr>-P MO's from adjacent &lOins. U1d exWidcd boncli"l.
Riehl: Band structure of a sin&le (Mn,P,E- layer. [Modified from Hoffmann. R.: Zhena. C. J . l'hys.
1985.89.
4175-4181. R epro<klc:ed with permimon.J
F;g. 7.30 Total DOS of the

extended
layer.
The rdalive c:ontribu1ions
of the m:lll,anese (clark

area) and the phosphorus
(liaht area) are indicaied.
N01e that the bondi,.
states 81 - 19 and - IS eV
are dominated by the

phosphorus. that ill. there is
more electron density on
the
than on the
(From
Hotrmann. R.: Zhc111. C. J.
Pltys. Clt ..m. 1985. 89.
4173-4181. Reproduced
with permission. I
-22
DOS -
Now. whal can we say about the phosphorus-phosphorus interaction between

layers? Comparing the layer structure
with the unil cell in Fig. 7.28, we see
thal the J-0 structure of BaMn1 P2 consists of alternating
and Ba2 + layers.
This brings the apical phosphorus atoms of one layer cb;e 10 those of the next layer.
and they interact along the l axis. If we look at the DOS for a single
layer (F.g.
7.30), but now inquire as to the contribution of the phosphorus Jp: orbital, we see that
:.
Solid-State MaJeriols with Polor Bonds
-4
-6
-a
....................
....,.,.........
.-:.::........ .........,.
- 10
..................
-12
283
Fig. 7.31 Phosphorus 3p:,

or1lilal contriblnion (dark
area) 1o the 1otal DOS
(clashed line; cf. Figs. 7.29
and 7.30) of the (Mn,P2fi
layer. (Modified from
Hoffmann. R.; Zhel\8. C . J .
l'lrys.
1985, 89,
4175-4181 . Reproduced
wilh permission. )
................. ......... .......

. . . ..:::
(eV) - 14
-16
-II
- 20
-!2
..-_...-_....,.
-
oos -
mosl (70"tl of it is in a rather narrow band at - IS eV (Fig. 7.31). The narrowness of a

band is an indication ofits localization: these are the lone pairs that were postulated on
the basis of the :PF; analq:ue (page 278). If these orbitals are completely filled, the
lone pairs on adjacent layers will repel each other. If half filled , they could fonn interlayer covalenl bonds. When the layers come toeether, we expect lhe P 1p, orbitals lo
interact strongly with shifts to higher (antibonding) energies and lower (bonding)
energies. In fact, all orbitals of the system with t components will interact. but only
the P3p, orbitals will be sufficient ly close 10 have much overlap.
The threwmensional (total) DOS is illustrated in Fig. 7.32. We see a lowlying
band at - 16.S eV corresponding essentially to a P- P bonding interaction and
Frg. 7.32 Phosphorus 3p,
conlribulion (dark
oreal 10 lhc 101111 DOS
(d8llhed line) of 1he 1hree
dimensional (lolal)
[Mn,P2
lallice. The P-P
inleraclions are labeled u
and
The square brackel
encloJes lhe bancls arising
principally from Jhe
manpne$0 3d orbitals.
[Modified from Hoffmann.
R.; Zherc. C. J . Phys.
1985. 89, 411$-41Hl.
l!"
u.
Reprodua:d with
permission.I
oos-
284
7 1M Solid State
another at -6 eV that is essentially n P- P antibording interaction. If only the lower

band is filled, we shall have P- P bonds between layers: ifboch ure filled there will be
nonbooding (van der Waals) contacts.
We must now compare how these bands lie with respect to the energies of the
electrons in the bands arisi11g from the metal 3d orbitals. The bottom and top of the 3d
band and the Fermi level change as one progresse.s across the transition series:.
There are two factors involved. The fraction of the band filled with electrons increases
with each increase in atomic number and addition of a valence electron. At the same
time, the level and width of the band decrease as u resuk of the increase in effective
atomic number. (Recall that d electrons shield poorly.) The overall result is a slow
lowering of the Fermi levd from Mn to Cu. Now if we superimpose the calculated
levels of the <Tp_p and the
interactions (Fig. 7.32) upon the Fermi level diagram,
we note an interesting difference between early and late transition metals:
u:-P
bonomor
...
dbancl
-a--a
Cu
77
Macltlnlolh. A. R.; Andencn, 0 . K. In Eltctrons Qf tltt F#Fmi Surfo<:t: Sprircford. M. Ed.;
Cambridae Univeoity: C.mbridae, 1980. Andoncn, O. K . In Tltt Eltclronk Srrur:turt o{Ccmplt r

Systmtr, Plwiseau, P.; Temmennon. W. M.. Eds.:
Plenum: New Yort. J<Jll4. Alldenen. 0 . K. In

lt/QfttrTNtN7; Bauani. F.; F...V, F .:Tossi, M. P .. Eds.; N<Jtti>.Hollud:
New Yod. 191.5. Vanna. C. M.; Wolson, A. J. Pity. Rn. 8: Condt M. MotttT 198t, 1112, 3m.
Solid-Slate Materials witt. Polor londs
215
The P- P band is u/woys filled, corresponding to :1 P-P bond (2lS pm) in the copper
compound. At the other extreme. the P-P" band Is also filled. giving an antibonding
interaction in addition. Thus, overall. there is a nc>nbondt!d interaction between the
two phosphorus atoms and so we should not be surprised that the P-P distance is
approximately twice the van der Wnals radius of phosphorus (2 x ISS pm - 384 pm).
We can view the progression from Mn to Cu as a redox luning the occupancy of
these energy levels:l8
or
.,\
.,. p-p .......
.,. p
-2<:
<3 0
..
p'
(7.8)
We see that our inruilion concerning the oddly

phosphorus atoms. that
they seemed to resemble phosphorus atoms in discrete molecules, has borne fruit.J9
High-Temperature
Superconductors40
SUperconductivity was discovered in mercury melal in 1911. Below 4.2 K lhe resistance of mercury drops to uro. Currently much interest is focused on hightemperature superconductors such as YBa1Cu30 7 _ 6 In this case. "high-temperature" is about 100 :!: 20 K. sreater than the boiling point of nitrogen (TI Kl. but
much lower than climatic temperatures on Eanh. Earlier superconductors needed to
be cooled by the mot"e expensive and difficultly handled liquid hdium (bp = 4.3 K).
Superconductivity has generated much excitement in the popular press because the
Mt!issnt!r t!/It!cl iDustrared by the now familiar picture
a magnet
over the
superconductor.
The first breakthrough superconductors were formulated as
(x < 0. 2, 6 unspecified but smaU) and have the tetragoi'IOII. Iayered
perovskite
structure. They had a critical temperature
a bout JS K. 41
Observation that the crilic:ll temperature increased with pressure suggested that it
depended upon lattice distances. Therefore strontium (r .. 132 pm) was substituted
for barium (r+ - 149) with some increase in
but dramatic improvement occurred
when Y (r. - 104 pm) was substituted for La (r+ "' 117 pml. and :1 new type of
compound, YBa2 Cu30 7 8 , was rorrned.4 l This is the so-c:llled 1-2-3 superconductor
or
or
or
"' HcK gain. both Ihe dipllosphol':lnclype sy,.crn on lllc len and I he anion.c s tNCtur.. un the rial>
nrc unknown in simple pllo"""""'s
bul S1F10 I known .
:10
the.c "'" rCiUOOahk:
struc1ures.
"'For del ails ol' lhc a>lculalions lllldlhcir inteCJ"'Ciali<Jn. """ Footnote )4
.,. Wh.111bo. MH.: Tor:>tdi. C. C. Att. Chrm. Rr1. t,l ,/4. 127- lll. Williams . J . M.: Bcno. M. A. :
Carlson. K. D .. Geiser. U.: Kao. H. C. 1.: Kini, A. M. : Poncr, L. C .:

A. J.: Th<lrn. R. J.:
W311B. H. H.: Whan&bo. M-H.: Evain. M. AC"c. Chrm. Rr1. 1988. 21. 1- 7. Holland, G. F.: Sexy. A.
M. Ibid. t988. 2/, &-IS. Ellis, A. B. J. Cht'm. Jo1C". 1987, 64.
4 ' See Jacob. A. T. : l'<lmann, C. t. : Elis. A. B. J. Chrm. &Juc. 1988. 6S, 1094-tm: Gum. M.:
Porter. J . Nrw Scirnl . 1988, 118 ( 1618).
.., Bednarz. J. G.:
K. A. Z. Phy. B.: CoiNh-M. Mottrr 1986. 64. tts<J. By loday"s nul'nb<-r>. 1his
was noc a tarae increuc: ower previous values (23 K ror a nid>ium alloy). bul a1 1ha1 lime it was
a
new dass d l!llllerial.< for I he saucly d supcn:ondu<
rdalively Jorxe. and il
livily. Bcdnorz and MDkr WCK awatdcd Ihe 19V? Nobel Pri:te in Physic.s . Their IICCCplanee kciUK
is 8ednon, J. G.: MOller. K. A. R,.;. MoJ. Ph.Y 19ll8. 60.
4J Wu, M. K.: A.hbum. J. R.: TOn1J, C. J.: Hor. P. H.: MenJ. R. L: 0..0. L : Hu:ona. Z. J .: Wan&. Y.
Q.: Ow, C. W. Phys.
Lnt. 1917. Sl. 908-910. The vakoes of ionic I'3Ciii on: from Table 4.4 and
areforC.N. 6.1n lhc:perovskite ruc:ture 1he C.N. 8 ror Y and to ror Ba.sowcc:1111 upt 1he
ims IO be aboo.ol 10'.0: latJcr.
286
7The Solid Stale
(from the ratio of Y-Ba-Cul. and perhaps is the best studied. II may be prepared by
various methods, but the pHadjusted precipitation and high-temperature decomposition of the carbonates is typical:
2Y3
+ JHCO)
..=.!(. Y2(C0,)) l
Baz+
+ HCO)
..=.!(. BaC03 l
(7.10)
cu2 + HCO) ..=.!(. CuC03 l
(7.11)
Y2CC03h + 4BaC03
(7.9)
2YBa 2Cu30 7 _ 8 + 13C02 t
+ 6CuC03
(7.12)
Other procedures stan with the oxides. or mixtures of oxides and carbonates. The rate
arul conditions of cooling are also important.
The 1-2-3 superconductor has a perovskite-like structure (7.33a,c). There are
systematic OXYI!Cn atom vacancies in the unit cell compared 10 a stack of simple
perovskite unit cell. (Fig. 7.33b). These occur between adjacent copper atoms in the
chains along the r axis. The vacancies are in the yttrium atom plane. There are also
vacancies between copper atoms along the a axis in the copper-and-oxygen planes
A
...
6
\1
.,.
0& fm
Cu
II
Iii'
L.o"
LP'
0
LP'r-- LP'
0
>...!.
lA
[/
II
lA
Tl
r.r-,
LP'
0
f:=- lia'
Cu2
ro2
0
'J
Cui
01
(C)
Fig. 7.33 cal Unit cell of the 1-2-3 superconductor. orthomombic. spnce aroup Pmmm. Qne-dimeNiional cu<>, chains run
alOne the b axis. and tWCH!imensional CuO: layers lie in the ob plane. (bl The cubic structure of perovsl<ite . S;TiO, . Three
unit cells are shown scacked vertically. (c) The unit cell of the 1-2-3 superconductor in the context o( the surrounding
crystal. Copper atoms are st.nounded either by five OXYB<n atoms in a square pyramid or four oxyacn Moms in a square
pbnc. (From Holland, G. F.; Stacy. A. 1\1. Acr. Chrm.
1988, 2/, 8-IS. Reproduced with permission .)
.. The
of thc$e supcn:onck.Cic>rs is still mud> of an art with 8f1ndq. hc:llina:. annealing or
slow cooling, etc., and each lab has ils own recipe. Mixtures ue ollcn formed with different pllases
present. Pn>ccdures :II'< aivcn in FootnOics 40. 41, and in Por1er, L. C.; Tbom, R. J.; Geiser. U.;
Umczawa. A.; Ware. H. H.; Kwolt. W. K.; Keo. H.C. 1. ;
Ill. R.; Cnlltrcc, C . W.;
Cutson. K. 0.; Wiliams. J . Ill. 1110'1(. Chtm. Jn'T. 16. 1645-1646; EniJcr, E. Ill.; Lee. V. Y.;
Nazzal. A. 1.; Bcycn, R. B. ; Lim. C. ; Cr.w. P. Ill.; Patlcin, S. S. P.; IWnira. Ill. L.: V;uqucz.
J. E.; Savoy. R. J. J. Am. Chtm. Soc. tm, /()9, 2848-28-19; Carbausltas. Ill. F.; Green. R. W. ;
Arendt. R. H.; Kasper. J. S. ltw<t. Chtm. 1,..,17, 871-873.
Solid-Stole Mote<iols with Polar Bonds
287
that
between the planes of barium atoms. The structural unit that is thought to be
responsible for the superconductivity is the
slab. The odd stoichiometry.
results from additional oxygen vacancies (defect structure) at the 01
and 02 positions such that 0.0 < 8 < 0.4; usually 8 .. 0. 19.
More recently, other metals such as thallium, bismuth, and lead have been
included in superconductor formulation. In one interesting series, the critical tern
perature has been found to increase with increasing n in susperconductors of the type
TIBa2 Ca,_ 1Cu,O:!Jt+! to a maximum of 122 K for n 4 (Fig. 7.34).45 The current
maximum critical temperature is 125 K for a closely related
The following generaliZlltions can be made about all of the high-temperature
superconductors examined to dat e: (I) The structures can be derived by stacking
different amounts and sequences of rock salt and pe,r ovskitelike layers of metal and
oxygen; (2) superconductivity occurs in the Cu01 1ayers ; (3) the similarity in energy
between the copper 3d and oxygen 2p levels causes them to milt extensively in the
electronic band at the Fermi level; (4) the non-Cu02 layers (part of the Cu01 chains in
the 1-2-3 compounds, the 11- 0 and Bi-0 layers in others) furnish electron density
that tunes the electronic state rl the Cu02 1ayers.44 Oellliled discussion rl superconductivity theory or rl band theory applied to these crystals is beyond the scope of this
n4
Fig. 7.34 Unit cells (wilh idealiUd atomic

of lhe firs1 four memben ollhe hOmok)QoU$ series
TIB:a:Ca_ ,eu.o..,.,. [From Haldar, P.; D>en. K.: Mwshwal'llll. B.; Roit-Janiclti, A.; Jaai. N. K.; Markiewicz, R. S.:
Oiessen. B. C.
t988.Z41. 1198-1200. Reproduced with permission.)
"' tbldat. P.; Chen. K.: Mahcswann. B.: RoiJJaridti. A.;JQaci. N. K.: M:ortiewicz. R. S.; Gieuen.
B. C. Sciftl<'r t"'- l4/, 1198-t200. For a discussion with many
ohhc variouuupcn:onductor
sec MOict-Busehbaum. H. A...,...,. Cl>mt. Int. &,1. E.d. 1919. 211. 1411-t493.
46 Cava.
R. J . Sdnw:' 1990,147. 656-662.
288
7 lM Solid Stole
text (but see Problem 7. 13), but it may be noted that these compounds are testing both
experimental technique and basic theory.47
Problems
7. 1 Find the spinel exceptions to the structure ftetd map in fig. 7.4.
7.2 Predicl the structures of the fOllowing (i.e ., to wh:lt minernl classes do they belong?):
a. MgCr,P.
b. K, MgF.
7 .J Rationalize 1he fact1h:lt the nuori1e ftcld lies above and to the riahl of t he rutile ftetd (f ig.
7.5) from what you know abou1 1hese structures. Doe.s this ii\Siglll ennbte you to predict
anylhina about the silicon dioxide st ructure?
7.4 Wit h regard touch or 1he foaowina. does it make ony difference whether one uses correct
radii, such as empirically derived Shannon- PuwiU radii, or whether one uses theoretically
reasonable but somewhat misassi111ed traditional rndii?
a. prediction of the imerionic distance in a
IIL'W
compound, MX.
b. calcutuion or the radius ratio in M, X .
c. calculalion or the enthalpy of rormalion of a hypothetical compound, MX1

d. construction of a structure field mop as shown in f'JiS. 7.4 and 7.S.
7.5 Why is graphite asood conduclorwhercas diamond isnoc?(Botb contain WiniJc taJtices or
covalently bolnl carbon atoms.)
7.6 It was stated casually

27S) thai the cncJSY levels of l;lllium are above those of
sermanium and. lata. that 1hose of anenk lie belOw those orse.r manium. Can you provide
any araurneniS. data, de., to subsuntiatc this?
7.7 Cadmium sulfide is oOen used in lhe photomclcrs of cnrncra.s to measure 1he available
visible Iicht. Suppose you were lnttte$1ed in infrared phoiOif"Phy. Usins fie. 7.25. sugdt
some compounds th:lt misht be suitable for an infrared photoccU.
7.8 Usina Fig. 7.25. calculate the wa\lelenath or tight at which phoiOCO<Iduction wiD begin for a
CdS lisht meter. If you are interested in black and white
can you leD why 1his
wavelenglh is particulllly approprinte?
7.9 A very imponant photographic rtaelion is 1he photolylie decompo5ilion of silver bromide
described approximately by I he followina equation:
AgBr(s)
....!!:...
Ag(s)
IBr,(ll
(7.13)
Assuming thai lhc emhatpy of the reaetion described in the equation ean be equated with
the energy 1he photon.
a Bom- HabeNype cyele 10 calculnle the wavelength oflisht
that is sufficicmly encrseic to effect the decomposition of silver bromide. What arc some
sours of error in your estimate?
or
use
7.10 There are two slructures illustrated by fiaures in this ehapcer that are not identified as being
the same, althou&Jl they depict the same crystal structure. Examine aU 1he crystal struc
lures in this chaplcr and identify t he two figures tha t are the same Slruclure.
7.1 1 Convince yourself that irt.here were no defect vacancies in the 1-2-l supe7conducting slob.
its empirical formula would be
7.12 If you are cenain that the 1ruc fonnula of the 1-2-3 supe7conductor is YBa,Cu3o,_. with
0.0 < & < 0.4, what does lhat imply cOncerning lhe copper atom.?
41
Wflansbo, M.H.: vain, M.: Bcolo. M. A.: Willi:lms, J . M. IMrr.

t981,26, 1129. Ill I, IIJl.
Malsen, f . A. J. CMm. EJ./c. 1917. 64, 841. Bwclclt, J. K.. In
itt CDor&u>liMr
Clw,Utry; W'tliams, A. f .; Flori.Jni. C.: Mctbedl. A. E., Eds.: VCH: New Yorlt, 1m.
Probl-
289
7. 13 To follow up on Problem 7. 12. the bnncl $lructure arising from the copper 3d orbilals hB$
been cnlcullltcd 10 be:
- It
i - '
e V
F
- 12
The .t> - y> bund lies in 1he CuO, 1:1yer.1 (11b pl:lne between the 8a nnd Y atoms). and the
l: - Y: band lies along the CuO, [CuO,-Cu0,-1 chains (b :uis between adjacem Ba
atoms). WhaJ can you say about 1he electron densi1y on the different Cu
!See
Foocnotes 40. 47.)
7.14 Slishovite is a dense. mctaslable polymorph of SiO, wi1h a C.N. ; 6 for silicon. It fQml$ at
pressures above 8.S GPa. In the meteoritic impacl vs. vulcanism comrovcrsy over the
nonconformity at the Cretaceous-Tertiary boundary ("What killed the dinosaurs?""). the
presence of $tishovile ac the K/T boundary has been used as an argument in favor of
meteoritic impac1 r:llher than volcanic activity (See McHone. J . F.; Nieman. R. A.; Lewis.
C. F.; Vales, A.M.
1?89. 14), I 182-1 184). OiSCU$5 the po$Siblc dtanges involved
in I he quuntlo-stishoviu:"" phase 1ramitions in terms of heat and pressure. and how lhey
relate to mc1eorites vs.
(See abo Sigurdsson. H.; O' Hond1. S .; Ar1hur. M.A. :
Bra1ower. T . J .: locho$. J . C.; von Fossen. M.; Channell. J. E. T. Nut"'" 1991. )49.
482-487.)
Quartz has C.N. 4 for silicon. much
Chapter
8
Chemical Forces
In the preceding chapters attention has been called to the importance of the forces
between atoms and ions in determining chemical properties. In this chapter these
forces will be examined more closely and comparisons made among them. The
important aspects of each type of force are its relative strength, how rapidly it
decreases with increasing distance, and whether it is directional or not. The last
property is extremely important when considering the effects of a force in determining
molecular and crystal structures. Because distance is an important factor in all
interaction energies, a brief discussion of interatomic distances should preface any
discussion of energies and forces.
ln1et'nuclear
Distcmces and
It is valuable to be able to predict the internuclear distance of atoms within and

between molecules, and so there has been muc.h work done in attempting to set up
tables of "atomic radii" such that the sum of two will reproduce the internuclear
Atomic Radii
distances. Unfortunately there has been a proliferation of these tables and a bewildering array of terms including bonded. nonbonded, ionic, covalent. metallic, and van der
Waals radii, as well as the vague term atomic radii. This plethora of radii is a reflection
of the necessity of specifying what is being measured by an atomic radius. Nevertheless, it is possible to simplify the treatment of atomic radii without causing
unwarranted errors.
Van der Waals Radii
If two noble gas atoms are brought together with no kinetic energy tending to disrupt
them, they will "stick" together. The forces holding them together are the weak
London dispersion forces discussed in a later section (pages 299-300). The internuclear distance will be such that the weak attractive forces are exactly balanced by
the Pauli repulsive forces of the closed shells. If the two noble gas atoms are identical,
one-half of the internuclear distance may be assigned to each atom as its nonbonded or
van der Waals radius. Solid argon (Fig. 8.1). for example, consists of argon atoms
spaced at a distance of 380 pm yielding a van der Waals radius of 190 pm for argon.
Although the van der Waals radius of an atom might thus seem to be a simple,
invariant quantity, such is not the case. The size of an atom depe.nds upon how much it
is compressed by external forces and upon substituent effects. For example, in XeF4
290
ltuemucleor Distances oncl AtoMic Roclii
291
Fig. 8 . 1 Unit cell of arson . Note that the c:onncctina lines are for
perspective only
do not repre$Cnt bonds. (From Ladd, M. F. C. Structur' ottd Bottdittg in Solid Stair
Chrmistry; Ellis Horwood: Chichester. 1979. Reproduced whh permission.]
the van der Waals radius of xenon appears 10 be closer 10 170 pm than the accepted
value of 220 pm obtained from solid xenon. The explanation is that lhe xenon is
reduced in size because electron density is shifted to the
electronegative fluorine
atom. In addition, the partial chatges induced (Xe&.. , f&- ) may cause the xenon and
fluorine atoms to attract each other and approach more closely.
Althuugh we must therefore expect van der Waals radii to vary somewhat depending upon the environment of the atom. we can use them to estimate nonbonded
distances with reasonable success. Table 8.1 lists the van der Waals radii of some
atoms.
Ionic Radii
Ionic radii are discussed thoroughly in Chapters 4 and 7. For the present discussion it
between ionic and van der
is only necessary to point out that the principal
Waals radii lies in the difference in the olfractivt forct, not the difference in rtpulsion.
The interionic distance in LiF, for example.
the distance at which the
repulsion of a He core (IJ+) and a Ne core (f- ) counterbalances lhe strong elec
II'Olitatic or Madelung force. The attractive energy for u F - is considerably over
SOO kJ mot- and the London cnel'l)y of He-Ne is of the order of 4 kJ mot- . The
forces in the IJF crystal are therefore considerably greater nnd the interionic distance
(20 I pm) is less than expected for the addition of He and Ne van der Waals radii
(340 pm).
Covalent Radii
The internuclear distance in the Huorine molecule is 142 pm, which is shorter than the
sum of two van der Waals radii. The
obviously comes from the fact that the
electron clouds of the fluorine atoms overlap extensively in the formation of the F-F
bond whereas little overta.p of the van der Waals radii occurs between Ihe molecules
HDmitlon, W. C.; Jbcrs, J . A. In NoblrG4s Com()Qundr. Hyman, H. H. , Ed.; Univ=ity dCbic:aCO:

Chicnao. 196); pp 19$-202. Templeton. D. H.; bllcln, A. ; Forresttt J. D.;
S. M. Ibid.
pp20J-210. Bums,J. H.; Avon. P. A.; IAy. H. /bid. pp211-220. In XcF. the xcnort:Jtoms do noc
touch each other. The csNnole d the""" du Waals r:tdius must be made by subtractU.Ihe """du
Waals radius of lluorinc from lhc shortesl nol'lbororkd (i.e .. bttwmo rnolccuk$) .-..-lluorinc
distan<:e 020-J)O pm).
Table 8.1
Alomic raclli lnod multiple bonding .,...-.., (pm)
sI.
2.
3.
4.
H
He
Li
Be
.5. 8
6. c
7. N
8. 0
9. F
10.
II.
12.
13.
.14.
IS.
16.
120"-145"
180'
180
Ne
Na
Mg
AI
Si
P
17. Cl
18. Ar
19. K
20. Ca
21. Sc
22. Ti
23.
24.
2S.
26.
27.
28.
Cr
Mn
Fe
Co
Ni
165"-170"
ISS
ISO
ISG-160
160'"
230
170
2 10
185
180
170-190
190'
280
,_.
90(+ I)
.59( +2)
41(+3)
126( -2)
119( - I)
116( +I)
86( + 2)
68(+3)
170( - 2)
167( -1)
152( + I)
114( +2)
88(+3)
74(+4)
140
140
190
36. Kr
200'
190
ISG-200
37. Rb
38. Sr
73
71
(69)
IS4
14S
130
118
110
102
99
(97)
196
184( -2)
182(-1)
120
120
122
122
117
114
110
_.
,...,..
C lfq.U)
104(+3)
44. Ru
3.5
38
4S
43
4S. Rh
46. Pd
47. Ag
48. Cd
49. In
so. Sn
Sl .
.52.
.53.
S4.
SS.
31
32
29
28
Sb
Te
I
Xe
160
170
160
190
220
108( + I)
109( +2)
94( +3)
2 10
195-212
220'
Cs
S7.La
207(-2)
io6( - l)
71. Lu
72. Hf
73. Ta
74. w
75. Re
76. Os
77. lr
78. PI
79. Au
80.Hg
81. 11
28
20
31
27
26
200
82. Pb
200
45
4S
171>-180
170
ISO
lSI(+ I)
116(+2)
102(+3)
83. Bi
84. Po
8S. At
86. Rn
22
3S
140
143
13S
133
130
18 1(+ I)
149f+2)
117(+3)
100(+3)
.56. Ba
139'
129
126'
12 1(Td)"
li6(Sq)h
91(+ I)
88(+2)
76( +3)
Element
39. y
40.1;
41. Nb
42. Mo
43. Tc
(32)
134
125
90
77
7S
160
29. C u
30.Zn
3 1. Ga
32. Ge
33. As
34. Se
3S. Br
C (Eq. 8.4)
'51
(14.5)
92. u
190
Organic groups
CH3
zoo'
C 6 H, 11Cf1
27
166( + I)
132( +2)
Values of van dcr Waals r.xlii from Bondi. A. J. Phy.
1964. 68. 441. unless otherwise noted.
Ionic: nodii (C.N. 6) are from Table 4.4 and are lisJed for comparative putpOses <riy. For additional values, see!Mt table.
Covoknt radii estimated from homonuclear bond Jal&ths whcte available and rrom sdeclecl hetcronuclear bonds olhetwise.
Bond ltngdls from Tobks of lnt.rtomlc
and Collfisurotion in Mokruln and
Suuon. L., Ed.; Spec. Pub!. Nos.
II and 18; The Cbemical Society: London. 1958. 1965, e.<cq>t where noted. Vaktcs In puenlheses are for noble psu not known
10 form compounds and are
from the values of
noametals: Allen, L. C.; Huheey, J . E. J. lnof'K. Nud.
Chm. 1910, 42, IS2J.
N. L. AllinJCr. Hlndl, J . A.; Miller, M. A.; Tyminski, I. J.; V-<:alleds-. F. A. J. Am. Clrm. S. IMS, 90, 1199.
Cook. G. A. Argon. Hdum onJ thr Rtur G<Jus; Wiley Untencienc:c): New Yoric, 1961; Vol. I, p 13.
F Cocton, F. A.; Riclwdson, D. C. lnorg.
L. F.; Rodulfo de
I H6. .S. 1851.

R. i>. J. Am. Chrm. S.
E.;
T.: PoweD, H. M. J. ci.iin.
1970, 1688.
'
91, 16S.S.
f)o
t hulina. L. 1hr Naturr qfthr CMmtcil &nJ, lrd ed.; Cornell University: Ithaca. NY, 1960.
- .::..=:=:. -
oo::.:::::..- :""-7
..
.3.
r .._
lternucleor Disto- oncl AtoMic Radii
293
F"tg. 8.2 lllustralion o1 the

difference between van der
Waals and c:Ovalent radii in
the F1 molecule.
T
(Fig. 8.2) because of the rapidity with which repulsive energies increase with decreasing distance. Now it migtlt be supposed that the equilibrium distance in the F 1
molecule is thai at which the maximum over1ap of the bon<lin& orbitals occurs.
However, if this were the sole criterion, the F 1 molecule would collapse.. until the
two nudei were superimposed. This would cause the orbital wave fUnctions to have
identical spatial distributions and the maximum possible over1ap. Obviously this does
not occur because of repulsions between the two positive nuclei. and repulsions
between the inner electron core and the electrons of the other atom. We can estimate
the radius of the He core (Z - 9) bY using Pauling's estimate for the isoelectronic F 7 +
ion. 1 pm. z To this we add the radius of the overlapping ortlital from the second F
atom. For the latter we can use the van cler Waals (VOW) radius of fluorine ( ISO pm.
Fig. 8 .2. almost certainly too large) or the ionic radius of fluoride (119 pm. Fig. 8.3a,
probably too small). The F(He}-F- (or (He)-Fvow> distance will be about 130
Nnof
HI cote ond bondina
t--lr, --t
lbl
Fig. 8.3 (a) Hypothetical FF- ioopair molecule illustraliQI repulsion betw""n the inner He
core and the "'lone paw ol the " F- ion." (b) More realistic rc.presentation or repulsions
between innef" core and valence shcl) electrons. (The He core is not dnwn to scale in either
sl<etdl.)
> ....... L. 1M NDIJirt

Ocmkd &nd, Jrd cd.; Comdl University: llhacl. NY. 1960: p5t4.
TIU a.ssames lhaJ 11>e liu olthe He core wiJ be unalrcctcd by pcMIIalion d ll>e 11 and 1p eloclrons,
which is not quile INt.
2414
I .Che mical Forces
( 160) pm. The experimental bond distance in F2 is 142 pm. about halfway between the
two admittedly crude estimates. Corresponding values for the other halogens are 190
(210) versus 199 pm for Cl. 220 (230) versus 228 pm for Br. and 2SO (260) versus 267 pm
for I. This is not meant to imply that the covalent bond in F2 i.s either an ionic F+ F- or
a van der Waals (He) .. F; it isn't (see Problems 8.30 and 8.31). The point here is not
the crude estimation of values easily obtained experimentally, but the physical model
that explains why the covalent radii of the halogens are 71. 99, 114, and 133 pm.
respectively. The chief factor in determining the covalent radii of atoms is the size of
the core electron cloud beneath the valence sheD. This might be loosely termed the
.. van der Waals radius of the core.
Table 8.1 lists covalent radii obtained by dividing homonuclear bond distances by
two. In many cases the appropriate homonuclear single bond has not been measured
and the assigned covalent radius is obtained indirectly by subtracting the covalent
radius of element B in a heteronuclear bond AB to obtain the radius of atom A.
The values in Table 8.1 are reasonably additive. that is. the covalent bond
distance in a molecule ABn can be estimated reasonably well from 'A + r 8 . Some
typical values are listed in Table 8.2. The agreement is fairly good. In the case of
molecules with several large substituent atoms around a small central atom such as
CBr4 and CCI4 , the crowding apparently causes some lengthening of the bond. There
are other cases in which the additivity of the radii is rather poor. For example. the
H- H and F-F bond distances are 74 and 142, respectively. yielding covalent radii
of 37 and 71 pm. However. the bond length in the HF molecule is not 108 pm, but 92
pm. If we assume that the size of the fluorine atom is constant, then the radius of
hydrogen in HF is 21. Alternatively. we could assume that the fluorine atom is
somewhat smaller in the HF molecule than in the F 2 molecule. an extremely unlikely
sit uation. Or more realistically, we can admit that the hydrogen atom is unique. that it
has no inner repulsive core to determine its covalent radius but that in bonding the
proton often partially penetrates the electron cloud of the other atom ano.l that the bond
distance is determined by a delicate balance of electron-nucleus
and
nucleus-nucleus repulsions. However, this does not really solve our problem. for a
widespread deviation from additivity results from the effect of difference s in electronegativity between the bonding atoms. h is usually observed that the bond length
between an electropositive atom and an electronegative atom is somewhat shorter
Table8.2
Comparison ol oclditiw
and experimental bond
distaecas (pm)
Molecule
Bond
HF
HCI
HF
HQ
HBr
HI
OF
BrF
BrCI
10
CH
CF
HBr
HI
CIF
BrF
BrCI
10
..
CH4
ca. '
C8r4
a.
'A+ re
108
lSI
170
170
ISS
214
213
232
00
114
148
-
CBr
19 1
_Cl
92
128
142
161
163
176
136
232
109 .
136 '
.,.
194 .
l11temudear Distances and Atomic Radii
295
than expected on the busis of their assigned covalent radii . Over fifty years ago
Schomaker and Stevensonl suggested the relation
(8.1)
where r is in pm. and t.x is the difference in electronegativity between a toms A and B
in Pauling units. Several workers have suggested modifications to improve the acJ curacy, but only one will be mentioned here. Portemeld has found that Eq. 8.2 is
somewhat more accurate and has a beuer theoretiC<!! justification:
(8.2)
The signifie<1nce of the bond shortening in highly polar molecules is reasonably clear.
Heteropolar bonds are almost always stronger than expected on the basis of the
corresponding homopolar bonds (see discussion of ionic resonance energy, Chapter
.5). The atoms in the molecule AB are therefore held together more tightly and
compressed somewhat relative to their situation in the molecules AA and BB. which
are the basis of the covalent radii. It is helpful to analyze the source of this stabilization somewhat more closely than merely labeling it "ionic resonance engery." To a
first approximation. it is caused by the extra bonding ene.rgy ('"ionic" or Madelung
energy) resulting from the partial charges on the atoms:
oo--
H,.-F'_
= -
41Tof
(8.3)
The difference in electronegativity between fluorine and hydrogen is about 1.8 Pauling
units, predicting a shortening of about 16 pm (Eq. 8.1). The exact tit with the
experimental data ( 108 - 92 = 16 pm} is fortuitous (Eq. 8.2 yields fJ.r = 23 pm}, and
the importance of these equations lies in the predicted shorte.ning and strengthening of
heteropolar bonds. This is an important aspect of covalent bonding.
For a polyvalent atom the partial charge builds up every time another highly
electronegative substituent is added. Thus the partial charge on the carbon atom in
carbon tetr.1fluotide is considerably larger than it is in the methyl fluoride molecule,
and so all of the C-F bonds shrink. though the effect is not as great for the last
fluorine as for the tirsa:
C-F(pm}
139.1
13.5.8
133.2
132.3
Peters has combined the Schomaker-Stevenson equation with Eq. 6.8, which
relates bond length to bond order. and obtained:
rAo =
rA
r0 -
IOjt.xl- (CA +Co - 17l t.xJ)Iogn
(8.4)
> Sdlomak..-. V.; Stevenson. D. P. J. Am. Chtm. Soc. 1941, 6J. l7-40.
Porterfield, W. W. l_.gtmic CMmlslry; Addiso<>-Wesley: Reading, PA. t984; p 167. and personal
communication.
J Pete<', L. J . C/wm. EJuc. 1986. 6J. t23.
296
8 Chemical Forces
c,.,
where 'A and r 8 are single bond covalent rudii. 3nd

1111d C8 ace unilless multiplebond parameters for each element (Table 8. 1). With a few notable exceptions. Eq. 8.4
gives reasonable estimates of bond lengths over a wide range of bond order and
electronegativity differences.6
This topic has been discussed extensively in Chapters S and 6, so only those aspect s
pertinent to comparison with other forces will be reviewed here. In general, lhe
covalent bond i.s strongly directional as a result of the overlap criterion for 11\a)(imum
bond strength. We have seen previously the implicnt!ons that this has for determining
molecular structures. In addition. the covalent bond is very strong. Some typical
values7forpurelycovalent bonds are P-P. -200 kJ mol- 1; C-C, 346 kJ mol- 1; and
H - H. 432 kJ
T he smaller atoms can effect better overlap and hence have
st ronger bonds. Bond polarity can
bond strength (cf. Pauling's electrooega
tivity calculations. Chapter S), 3nd so we find a few much stronger bonds such as
Si-F (which probably includes some 1r bonding as well), S6S kJ mot- . Homopolar
bonds between smaP atoms with repulsive lone pairs tend to be somewhat
than
average, for example. N-N, 167 kJ mol- 1,and f-F, ISS kJ mol- 1 Nevertheless. a
good rule of thumb is that a typical covalent bond will have a strength oc'about
250-400 kJ
As we shaP see, this is stronger than all otherche.mical interactions
with the exception of ionic bonds.
Because of the complexity of the forces operatins in the covalent bond. it is not
possible to write a simple potential energy fUnction as for the electrostatic forces such
as ion- ion and dipole-dipole. Nevertheless. it is possible to describe the coval(llt
energy qualitatively as a fairly short-range force (as the atoms are forced apart, the
overlap decreases).
Types of
Chemical Forces
Cova le nt Banding
mor .
Io nic Bo nding
The Strength of a purely ionic bond between two ions can be obtained quite accurately
by means or the
equation (Chapter 4).M Neglecting repulsive forces, van
der Waals forces, 3nd other small conltibutions, we can estimate the enersy of an ion
pair simply as
= zz-r2
(8.5)
41TI'o
For a pair of very small ions. such as u anti F -. we can estimate a bontl energy of
about 66S kJ mol- 1 The experimental values are S73 kJ mol- 1 (Appendix E) for
d issociation to ato ms and 76S kJ mol - 1 (S73 + .6.H1E(Li) + I!.HEACF)J for dissociation
to ions. For a pair or larger ions. such as cs 3nd ,-, the energy is correspondingly
We shall sc:e in Chapter t6 that some bonds, such or the Cr- Cr bond. on: panicularly sensitive to
the nalure the substituents.
or
Tables or bond en<flie on be (ound in Appendix E.

The " bond strencth" thus OOtoincd refers, or C:OUI'SC, IO the dissociot ion or the ion pair to the
a<par31ed ions. Mx- - M +
It is somewhat aticr to clissociote an ion pair W>to the
undlat&ed constituent atom.. Mx- - M + X. be<::>olle the iDniution netll' ofthemeUII is vcater
11-. the declron al!init y d the IIOniiKW.
x-.
Types of Chemical Forces
297
smaller or about half as much. It is evident that the strength of ionic bonds is of the
same order of magnitude as covalent bonds. The common notion that ionic bonds are
considerably stro,.;er than covalent bonds probably results from mistaken interpretutions of melting-point and boiling-point phenomena. which will be discussed later.
Ionic bonding is nondirectional insofar as it is purely electrostatic. The attraction
of one ion for another is completely independent of direction. but the sizes and
numbers of ions detennine crystal structures. Compared with the forces to follow,
ionic bonding is relatively insensitive to distance. It is true that the force between two
ions is inversely proportional to the square of the distance between them and hence
decreases fair1y rapidly with distance. but much less so than most other chemical
forces.
Jon-Dipole forces
The various factors affecting the magnitude of the dipole moment in a polar molecule
were discus:;ed in previous chapters. For the present discussion it is sufficient to
picture a molecular dipole as two equal and opposite charges (q =) separated by a
distance r'. The dipole moment. !J.. is given by
!J.
qr'
(8.6)
When placed in an electric field. a dipole will attempt to orient and become aligned
with the field. If the field results from an ion. the dipole will orient itself so that the
attractive end (the end with charge opposite to that of the ion) will be directed toward
the ion and the other. repulsive end directed away. In this sense. ion-dipole forces
may be thought of as "directional ... in that they result in preferred orientations or
molecules even though electrostatic forces ace nontlirectional.
The potemial energy of an ion-dipole interaction is given as
IZ"'II'L'
471Tl*o
(8.7)
whe.re Z= is the charge on the ion and r is the distance between the ion and lhe
molecular dipole:
1'1
0 0-0
L,._j
!on-dipole interactions are simil<sr to ion-ion interactions. except !hat they are more
sensitive to distance (1/r! instead of 1/rl anti tend to be somewhat weaker since the
charges (q+. q - ) comprising the dipole are usually considerably less than a full
eleclronic charge.
Ion-dipole forces are important in solutions of ionic compounds in polar solvents
and
(for solutions ofNaF in H!OI
where solvated species such
exist. In the case of some metal ions these solvated species can be sufficiently stable to
be considered as discrete species. such as [Co(NH.Jihll+. Complex ions such as the
latter may thus be considered as electrostatic ion-dipole inlcractions. but this oversimplification (Crystal Field Theory; see Chapte.r II) is less accurate than are alternative viewpoints.
298
8 Cltemicol Forces
Dipole-Dipole
Interactions
The energy of interaction or two dipoles9 mny be expressed as
E = -2/leJ.Il
(8.8)
41Trl(o
This energy corresponds to the "head-to-tail" arrangemem shown in Fig. 8.4a. An

alternative arrangeme.nt is the antiparallel arrangement in Fig. 8.4b. The second
arrangement will be the more stable ifthe molecules are not too "fat. It can be shown
that the energies of the two arr.mgements are equal if the long axis is 1. 12 times as long
as the short axis. Both arrangements can exist only in situations in which the attractive
energy is larger than thermal energies (RT = 2.5 kJ mol- 1 at room temperature). In
the solids und liquids in which we shall be interested, this will generally be true. At
higher temperatures and in the gas phase there will be a tendency for thermal motion
to randomize the orientation of the dipoles and the e.nergy of interaction will be
considerably reduced.
Dipole-dipole interactions tend to be even weaker than ion-dipole interactions
and to ran off more rapidly with distance (1/rl). Like ion-dipole forces. they are
directional in the sense that there are certain preferred orientations and they are
responsible for the association and structure of polar liquids.
Induced Dipole
Interactions
If a charged particle, such as an ion. is introduced into the nei8Jlborhood of an

uncharged, nonpolar molecule (e.g. an atom of a noble gas such as xenon). it will
distort the dectron cloud of the atom or molecule in much the same way that a charged
cation can distort the electron cloud or a large, soft anion (Fajans' rules. Chapter 4).
The polarization of the neutral species will depend upon its inherent polarizability
("softness"), a. and on the polarizing field afforded by the charged ion.
The
energy of such an interaction is
z:.
..
_! z21U'2
2
(8.9)
r4
In a similar manner. a dipole can induce another dipole in an otherwise uncharged.

nonpolar species. The e.nergy of such an interaction is
-p.1a
rh
(8.10)
where p. is the moment of the inducing dipole.

Both of these interactions tend to be very weak since the polarizabilitie.s of most
species are notlurge . Because the energies vary inverse.ly with high powers of r. they
are effective only at very short distances . Their importance in chemistry is limited to
situations such as solutions of ionic or polar compounds in nonpolar solvents.
00
(I)
00
(bl
Fig. 8.4 (at Headto-tail

arrangement of dipoles;
(b) antip311lllel am1ngement
0( dipoles.
one
'Mulliplying Eqs. 8 .5, 8.7, 8.9. and 8 . 10 by Avopdros

yidcls Ihe correcl cncf8Y foe
mole
or eac:.h species interacting. Since Eq. 8.8 involves two moln:Mks of the polar species. mu!eiplyill(! by
N yields the <n<rgy or two molts of di!>oles.
Types of CJ.e..,ical Forces
Instantaneous
Oipal-lnduced
Dipole lnteractionslo
299
Even in atoms in molecules which have no pennanent dipole, inslantlltleous dipoles

will arise as a result ot momentary imbalances in elecl ron distribution . Consider the
hdium atom, for example. lt is extremely improbable that the two electrons in the Is
orbital of helium will be diametricaDy opposite each other at all times. Hence there
will be instantaneous dipoles capable of inducing dipoles in adjacent atoms or molecules. Another way of looking at this phenomenon is to consider the electrons in two
or more "nonpolar" molecules as synchronizing their movements (at least partially) to
minimize electron- electron repulsion and maximize electron- nucleus attraction .
Such attractions are extremely short ranged and weak, as arc dipole-induced dipole
forces. The energy ot such interactions may be expressed as
-Zii<r
E=-;r
(8.11)
where ji. is the mean instantaneous dipole, or more c.o nveniently as

-3/al
=4;6
(8.12)
where a is the polarizability and I is the ionization energy of the species.

London forces arc extremely short range in action (depending upon 1/r6) und the
weakest of aU attract ive forces ot interest to the chemist. As a result of t he al term,
London forces increase rapidly with molecular weight. or more properly. with the
molecular volume and the number of polarizable dectrons.
It can readily be seen that molecular weight per se is not important in determining
the magnitude of London forces as reflected by the boiling points of H 1 , MW
2,
bp = 20 K : 0 2 , M W 4 (a factor of two d ifferent), bp = 23 K ; T:, MW e 6, bp
2S K-as well as similar compounds, such as hydrocatbons containing different
isotopes of hydrogen. Auorocari>ons have unusually low boiling points because
tightly held dectrons in tile fluorine atoms have a small polarizability.
Repulsive Forces
All of the interactions discussed thus far are inherently attractive and would become
infinitely large at r - 0. Countering these attractive forces are repulsive forces
resulting from nucleus- nucleus repulsion (important in the
molecule) and, more
important, the repulsion of inner or core electrons. At e xtremely short interatomic
distances the inner electron clouds of the interacting atoms begin to overlap and P:luli
repulsion becomes extremely large. The repulsive energy is given by
(8.13)
where k is a constant and n may have various values, comparatively large. For ionic
compounds. values of n ranging from 5 to 12 prove useful (Chapter 4), and the
Lennani-Jones function. ofien used to desaibe the behavior of molecules. is sometimes referred to as the 6-12 func.tion because it employs r6 for the attractive energies
oo Theoe are also sometimes
to as Lon<kn disp<nlon forcu or YOn tk Wauls forct. The

former name, althcuah widely used OnciLJdinc in ollis texo), is unfortunate ina. much as It
to
Imply oloaoI he forcu tend to "dispone" I he molecules.
they are alwllys llnoctive. U"'e
or the term "van du Waals forecs varies: Some auohon use it synonymousl y with London fon:cs;
others use it to melll'l all or the forc:a which cause deviation from ideal behavior by reai&OlleS. The
Iauer would include 1101 only London forces but also dipole int<r.>ctions, ck:.
300
BC...mical Forus
Table 8.3
Summary of doemKal forcn one! intetadions

TYPe ollnlerK!ion
Strength
Covalent bond
Ionic bond
!on-dipole
Dipole-dipole
Jon-induced dipole
Dipole--induced dipole
London dispersion fa"ces
VeTY sti'OC1g
Very strong
Strong
Moderately strong
Weak
VeTY weak
Very weak
Complex. but comparatively long range

1/r,
range
1/r2, short range
1/rl, short range
1/r, very short range
1/r6. ex1remely short range
1/r'>, ex1remely shOrt range
Since London fon:es incnasc wilh incfeasing size and 1hcre is no limit to lhc size
fon:ea can become
latJe. In gnneral, however, 1hey are very weak.
or mole<ulcs. these
(cf. Eq . 8. 12) and r12 for repulsions. In any event, repulsive e.nergies come into play
only at extremely short distances.
Sum mary
Various forces acting on chemical species are sununarized in Table 8.3. The forces are
listed in order of decreasing strength from the ionic and covalent bonds to the very
weak London forces. The application of a knowledge of these forces to interprCtation
of chemical phenomena requires a certain amount of practice and chemical intuition.
In general, the importance of a particular force in affecting chemical and physical
properties is related to its position in Table 8.3. For example. the boiling points of the
noble gases are determined by London forces because no other forces are in opera
lion. In a crystal of an ionic compound. however. although the London forces are still
present they are dwarfed in comparison to the very strong ionic interactions and may
be neglected to a first approximation (as was done in Chapte.r 4).
Hydrogen
Bonding
Although some would contend that hydrogen bonding is merely an extreme manifesta
tion of dipole-dipole interactions, it appears to be sufficiently different to warrant a
short. separate discussion. In addition. there is no universal agreement on the best
description of the nature of the forces in the hydrogen bond .
We shall adopt an operational definition of the hydrogen bond: A hydrogen bond
exi.st1 when a hydrogen atom is bondl!d to two or more other utoms.ll This definition
implies that the hydrogen bond cannot be an ordinary covale.n t bond since the
hydrogen atom has only one orbital (Is) at suflicie.ntly low energy to e.ngage in
covalent bonding.
Macroscopically the effects of hydrogen bonding are seen indirectly in the greatly
increased melting and boiling points of such species as NH3 , H 20. and HF. This
11
Hamilton. W. C .; lbers. J . A. HydrDfltn

in S<>lid.s; W. A. Beljarrjn: New York. 1968: p 13.
Similarddiniliono areolf..-ed by Pimonld. G. C.; McOcuan. A. L. Tlw HyJrDf1tn Bond; Freeman:
San F,..n<:isco. 1960; Jocsten. M. D.;Sct.ad. L. J.
BondinJI; Marcel Dekker: New YClCt.
1974; Tht Hy.}roKfn Bond; S.:husl..-. P.; Zundd, G .; Sandorfy. C .; Eels.; Nor1f>.Hollancl: Amster
dam. 1916; Vc)ls. t- Ill; Jdfrcy. G. A. ;
W.
BontflnJI In Bi<>logicol Stf'UCiurn;
Springtr-Vcrlq: New YCl<t, t991. See also Allen. L. C. J. Am. Chtm. Soc. 1975, <n.
Emsley, J . Chtm. Soc. Rtv. 1980, :s7, 91-124; Lcgon. A. C.; Milkn. 0 . J. Ch<m. Rtv. 19116,86,
635-657; Jocstcn, M. D. J . Clwm. due. 198Z, S9, 362.
s...,,.,.,
Hydrogen landing
301
phenomenon is well documented in introdUCtory texts and need not be discussed

fur1her here. On the molecular le vd we can observe hydrosen bondins in the greatly
reduced distances between atoms, distances that fall below that expected from van der
Waals radii. Indeed this is a practical method of distinguishing between a true bonding
situation and one in which a hydrogen atom is close 10 two atoms but bonded to only
one. Table g_4 lists some distances in hydrogen bonded A- H B systems compared with the sum of the van der Waals radii for the species involved. In many
hydroge.n bonds. the atoms A and B are closer together than the sum of the van der
Waals radii. Even more characteristic is that the hydroge n atom is considerably closer
to atom B than predicted from the sum of the van der Waals radii, indicating
penetration (or compression) of atom B's elec tron cloud by the hydrogen.
In the typical hydrogen bonding situation the hydrogen atom is attached to two
very electrooegaJive atoms. The system is usually nearly linear and the hydrogen atom
is nearer one nucleus than the other. Thus . for most of the systems in Table 8.4, the
hydrogen atom is assumed to be auached to atom A by a short, normal covalent bond
and attached to atom B by a longer, weaker hydrogen bond of about SO kJ mol- 1 or
Jess. This situation usually obtains even if both A and Bare the same element as in the
hydrogen bonding between oxygen atoms in water. There are important exceptions,
however. These include salts of the type M+HA} , where A- may be the ftuoride ion
(less frequently another halide) or the anions of certain monoprotic organic acids such
as acetic or benzoic acid. Alternatively, HAAH may be a diprotlc: acid such as maleic
or phthalic acid:
1)
T<>We8.4
Von dow Wools diotonces
and ob..,...ed distvnces (pm)
for same common hydrogen
bonds
A . I'
Bond type
(calc)
F-H-F
0-HO
0-HF
0 -H N
0--HO
N-H O
N-HF
N-HO
N-H N
N-H S
C-HO
270
280
280
290
320
290
A .. l
(abo)
H 8
H . 8
(cole)
(abc)
240
270
270
280
310
290
260
260
260
270
300
120
170
170
190
220
260
200
290
280
330
330
310
300
340
300
340
r
320
2.60
300
190
.: : 2AO
... 270 .. :0... t 220
310
2AO
260
( 2.30
Hamilloa w. C.; lben. J . A. Hyd"'fttl B<>Nifltt 1J1 Solltlt;

W. A. Be.Uam81: New Yew\, 1968; p 16. UNCI w1111 permbaioo
,..-r; "'}j
J t
... , .
The voluea In coUan 2 are not thOle to be oblalned by the 1

uoe ornble 8. 1 because Hamiltocl and l bers llled van da-
.... !.d
302
8 Chemical Forces
This type of hydrogen bonding is termed

in contrast to the more common
form. Symmetrical hydrogen bonds form in only the strongest bonded
systems. These are frequently onionic like FH F- nnd the carboxylates mentioned
above . An eXllmple of a strong. symmetric hydrogen bond in a cation is the
bis{N-nitrosopyrrolidinc)hydrogen cation {fig. S.S).:
Although the subject of symmetric versus unsymmetric hydrogen bonding has
received considerable auention. there is yet little undersumding of the factors involved. Cenainly. for the long, weak hydrogen bond we can approximnte the situation
by assuming the hydrogen atom to be co11alently bonded to one atom and to be
auracling the other. Ob11iously. it will be closer to the conlently bound atom than to
the dipole-allracted atom. It is not so easy to see when or why the bond will become
symmetrical. although if a resonance or delocali:zed molecular orbital model is inIIOked. an analogy with the equivalent bond lengths in benune can be appealed to.
The situation is more complicated than that, however. for
FHF- ions
are known in some crystals. ll In the same way the hydrogen maleate and hydrogen
phthalate anions. found to be symmetrical in the crystal, appear to be unsymmetrical
in the less ordered aqueous solution. Whether symmetrical hydrogen bonds are
forced by a symmetrical environment or whether unsymmetrical bonding is induced
by crystals and solutions of lower symmetry is, perhaps. a moot point
Since hydrogen bonding generally occurs only when the hydrogen atom is bound
to a highly electronegative atom." the first sunestion concerning the nature of the
hydrogen bond was that it consists of a dipole-ion or dipole- dipole interaction or the
son A,._ - HM- B-orA,._ - H&+ B..,_ - Ra.. where R is simply the remainder
of a molecule containing the electrorn:gative atom B. Sup pun rur this viewpoint comes
from the fact that the strongest hydrogen bonds are formed in systems in which the
hydrogen is bonded to the most electrone&ative elements:
F- + HF - FHF(CH3)zCO + HF - - (CH 3hCO HF
H20 + HOH - - H:O HOH (ice)

HCN + HCN -
HCN HCN
tJf - 161
:!:
(8. 15)
= - 2S kJ moJ - t
(8. 16)
AH - 12 kJ mol -
(8. 17)
f:J.H
n Keefer. L. K.: Hrabie. J. A .: Ohnnnc.;an. L.: Aippen-Andcrson. J. L.;

c. 1988. 110. 3701-3702.
"Williams. J . M.; Sch....,....yer. L. F. J. Am. Ch,.,. Sue. t973. 95. 57ll0.
lll.ll0 t0-8011.
Pcmn, C. L : Thol!urn. J. 0 . J. Am. Chrm. Su<.
s..
8 kJ mot- (8.14)'6
tJf = - 46 kJ mol -
C. J. Alii. Clwm.
" Even rather dec1roposi1ive elemerus such as carbon a>n tall'IC

hydrosen atoms 10 fonn
hydr0<n bonds. In HCN. for example. the effective tlectronqalivily ol 1hc t:lrbon is Slilt <:ompaOI.Iivety hiJh, the hydroJ<113lom is
and it ...ould be epeclc:d 1o hydroccn bond 1u the:
nq:otive ni1rocen oJomolan adjacent molecule. II hmia boitife point of2f>"C compared to:!tl"Cfor
HF and tOO c for H!O. Even in the melhyt croup ol CHlCN some h)drocen borl<lin& eM
3pparen1ty lake plocc since the:
point of I>Cdonitrile is hi;hu (82 "0 lhon cxpee1cd on
basis ol
moteeular
(London forces) alone: The boilinc point ot "..,.-oponc
-42 "C.
Acetonilrile is olso c:omplelely miscible Olil h water. See Green. R. 0 . H1drol:m &IJJUw by C-H
GrDups; Wiley; New Yorlt. t974; Muekr-Westcltlolr. U. T.; Naz:za1, A.: Prchsdorf. W. J . Am.
Clwm. Soc.
IOJ, 7673-7Q2; Oesirqju. G . R. An-. Clr#m. /Ws. 1,1. 24.
m t.
"'Lias. S. G.; &runess. J. E-: l.iebnwl. J. F.; H<*nes. J. L.: Levin, IL 0 . Maltord. W. G. J . Plly1.
Clwm.
l>GID
1988, 17. Suppt. I .
Hydrogen Bonding
303
F'og. 8.5 Shor1. symmeuic:al hyclroeen bond in 1he cation of biS(N nitrosopyrrolidine)
hydrogen hexalluorophosph:lte wtlich crystallites in the monoclinic space
P2ofc:. The
hydrogen bonded proton lies on o center of symmetry, with only one of the nitrosopyrrolidine
molecules being cryslul108'111>hically unique. Note th:lt the o-0 distMCe is only 247 pm
whereas two times the v:.n de.r Waals radius of oxygen (Table 8. 11 is 300 pm. [From Keder,
L K.; Hrabie. J. A.; Ohannesian. L ; Aippen-Anderson. J . L .: Georae. C. J . Am. Ch.,m.
Soc. 1988. 110. 3701- 1702. Reproduced w;lh permission.}
The simplistic electrostatic model qualitatively atcOUnts for relative bond energies and the geometry (a linear arrangement maximizes the attr:u:tive forces and
minimizes the repulsions). Nevertheless. there are rensons to believe that more is
involved in hydrogen bonding than simply an exaggerated dipole-dipole or ion-dipole
interaction. F'rrst. the shortness of hydrogen bonds indicntes considerable overlap of
van der Waals radii, and this should lead t o
repulsive forces unless
otherwise compensated. Secondly. symmetrical hydrogen bonds of the type
F- H- F would not be expected if the hydrogen atom were covalently bound to one
Huorine atom but weakly auracted by an ion-dipole force to the other. Of course. one
can invoke resonnnce in this situation to account for the observed properties:
F- H F- .._ F - H- F
This implies delocalization of the covalent bond over both sides of the hydrogen atom.
One might then ask whether a simpler molecular orbital treatment of the de.localization
would be more straightforward. The answer is yes . The mechanic.s will not be given
here (see Chapter 17. the three-center four-c:lectron bond). but the results are that the
covalent bond is " smeared" over : &II three
In symmetric hydroge n bonds it is
equa.l on both sides: in unsymmetric hydrogen bonds more elect ron density is concentrdted in the shorter link. Several workers have calculated and ana.lyzed hydrogen
bond energies. n T he interpretations are not identical, but all indicate strong contributions from both electrostatic (ion-dipole. dipole- dipole) and co\lalent (delocalization,
resonance) interactions .
Systematic ana.lyses of crystallographic data for hydrogen
have revealed a
range of geometries and have led to proposals for rules to
or predict
hydrogen bonding patterns.- An energetic preference for linear or near-linear
see Basch. H.: Stu,ns, W. J . J . Am. Clvm. Sue. t99l.IIJ. 9S- IOI: Dykslra, C. E.
A<'c. Clwm. Ru. 191lll. 2/.
Lqon. A. C. Clwm. Soc.
t990. 19. 197-237: Cla1iss.
L A.; BlaDder, M. Clttm. Rw. 191lll. M. 827-841 .
R. ; Kennard, 0 . Arr . C..tm. Rn. 1984, /7, 320-)2.6. Eucr. 1\4. C. A<"<". Qw,_Rt- -
21. 120-126. GilrbiiZ.. C. H.; Euer. 1\4. C. J. Am. C/oml. Soc. 1992. //4,627-631.
I& Taylor,
30'4
B CMmlcal Fotces
A- H 8 configurations, at least in the crystalline state. is confirmed by the

experimental data. Tile stereochemical requirements of hydrogen bonds determine the
structure of ice and lead to the well-known fact that solid water is less dense than
liquid Water at the melting point. This is because the structure of ice is rather open as a
result of an extensive network of hydrogen bonds (Fig. 8.6). Hydrogen bond energetics and stereochemsitry have wide-ranging implications in the areas of catalysis,
molecular recognition, and design of new materials.
Finally, there are othe.r systems such as W- H-W and B- H-B (Chapter 16)
which formally meet the operational definition of hydrogen bonding given above. They
atoms bonded to the hydrogen atom. To
differ, however. in having
distinguish them from the electronegative hydrogen bonded systems, they are ofien
termed
systems.
Hydrates and
Oath rates
The hydration of ions upon solution in water has been mentioned previously and its
importance to solution chemistry discussed. In the solid crystalline hydrates. hydrogen bonding becomes important in addition to the ion-dipole auractions .9 Often the
water molecules serve to fill in the interstices and bind together a structure which
would otherwise be unstable because of disproportionate si:tes of the cation and anion.
For example, both FeSiF6 6H1 0 and Na_Xe06 8H20 are well-defined. crystalline
solids. The anhydrous materials are unknown. Tile large. highly charged ani:ons
presumably repel each other too much to form a stable lattice unless there are water
molecules present. In ge.neral, some water molecules will be found coordinated
Fig. 8.6 The open structure of normal ice that results from the direclionality of lhr hydrogen
bonding. (From Oickenon. R. E.; Gcis. I. Ch. mi.ury. Muuu. ond th Univn<'; W. A.
Be'liamin: Menlo Pan. 1976 .)
,. Hamilton; W. C.; lbers. J . A. HydrDfrtt Bondinx in Solids; W. A. Beqjamin: New Yortt. 1968: pp
204-221.
Hydrogen Bondint
305
directly to the cation and some will not. All the water molecules will be hydrogen
bonded. either to the anion or to another water molecule.
A specific example of these types of hydrates is CuS04 SH20 . Although there
are five molecules of water for every CuZ+ ion, only four are coordinated to the cation,
its six-coordination being completed by coordination from
(Fig. 8 .7a). The fifth
water molecule is held in place by hydrogen bonds. o-H 0, between it and two
coordinated water molecules and the coordinated sulfa te anion (Fig. 8 .1b). Dehydra
tion to
CuS04 H 20. and eventually anhydrous CuS04 results in the
water molecules coordinated to the copper being gradually replaced by oxygen atoms
from the sulfate.20
An interesting hydrate is that of the hydronium ion in the gas phase. It consists of
a dodecahedral cage of water molecules enclosing the hydronium ion: H30.(H20hoEach water molecule is bonded to three others in the dodecahedron (Fig. 8.8a). Of the
various possible hydrates of H1o in the gas phase, H10+(H20ho is by far the most
stable.z
The dodecahedral structure may CMTY over into the solid phase. Note that half of
the oxygen atoms in Fig. 8.8a have their fourth coordination position occupied by a
hydrogen atom that can bond to adjacent polyhedra (Fig. S.Sb), and the other half have
a lone pair at the fourth position which can donate a pair of electrons to form an
external hydrogen bond (Fig. 8.8c). Thus in the sol;d, these dodecahedra can pack
together to form larger structures with rdatively large voids in the centers of the
dodecahedra. G11est molecules such as Ar, Kr, Xe, CH4 etc., may occupy these
spaces. These gas hydrates in which the gueat molecules are not bound chemically but
are retained by the structure of the host arc called clathrates. Since the structure can
exist with incomplete fillilll! of holes. the formulas of these clathrates are variable.
so;-
H
11'\,
C11
HH
so,
s of so!"
C11
O O;menof
o.,..... of so:
0 Oanco or fitch H,O
cOM!inalc4 H1 0
(a)
(b)
F19- 8.7 Structure or

pcntahydnW:. (a) COOC'dination sphere of cu>. four
-ter molcculcs and two sulfate ions; (b) Position of firth water molttule (oxyarn ""own by
,.,vy arck). Normal covalent bonds depcted by solid tiMS; o-H 0 hydroien bonds
c!epictcd by clashed lines.
Wdls, A. G.
11
SITIICturtllltttNifGniC Clwmittry, Sth cd.; O:wendon: Oxford. 1984; pp

Wci, S.; Shi. Z.; castleman, A. W., Jr. J, Cltrm. Pltys. 1991, 94, n61- Jl10.
306
8 O.mieal Fore
0
---0
/\
1\
Ill
(bl
1<1
Fig. 8.8 (a) Pe.n tagonal dodecahedron composed or twenty H.O

connected. by hydrOQcn bonds. (b) Apu of
dodecahedron with external hydrogen atom Cllp<lble of acceptina a lone pair rrom an a4Jacent polyhedron 10 form linking
hydro&Cfl bond. (C) Apex of dodecahedron with external lone
Capable of hydrogM bonding loa hydrogen in an adjacenl
polyhedron.
Hydrate clalhrates of organic compounds ate thought to be responsible for the

behaviorof"ice" in the heads of comets and in wet methane underpressure.n Unless
methane is carefully dried, high-pressure lines may become clogged with I he ice-like
gas hydrate. There may be large deposits of methane hydrates, "the ice that bums,"
beneath the ocean floor.
Not all clathrates are hydrates. Other weD-known examples have host lattices
formed from hydrogen bonded aggregates of hydroquinone, phenol, and similar
organic compounds. Non-hydrogen bonded host structures arc also known. One
example is a cyclotriphosphaz.ene. (C6 H40 2 PN),, that traps molecules such as benzene in tunnels in the crystaJ.n In addition. coordination polymers ate formed by
ambidentate ligands. such as CN - and SCN-. which coordinate to metal ions at both
ends (Chapter 12). Perhaps the best known of this type of compound is the series of
Ni(CNhNH3 M compounds, where M muy be benzene, thiophene. fumn. pyrrole.
aniline, or phenol.
Current inlerest in clathrate structures focuses on molecular recognition. a broad
topic that includes resolution of enantiomers (Chapter 12), maaocydic chelates
(Chapter 12), and key-and-lock enzyme activity (Chapter 19). In terms of clnthrates,
the challenge is to structure the vacancy in such a way that particular molecules will
be incorporated ns guests.z
D.; AIIIIIIUinclola. L ; Sandford. S.; HudJins, D.; Freund, F.

199t. 2$4, 543-SSI .
Appenzeller, T. Sci,tt 1991, 2J2, 1190-1197.
u AUccek, H. R. ; Allen, ft. W. ; 8i1Sdl, E. C.; Sm<llt. L. A.; Teeter, M. J, Am. CA,m. Soc. tm. 98,
:SJ20-:SI2$.
"Mokcular lndutioM and Mollclhr

I; Gctdil, R.; Web<r. E.. Eds. ;
Topics in Curftnl Cllemislry 140: Sprin...-.Yc:r1q: Berlin. 1987. Mt>llcullw lnchtsiolll and
lular R"alttilion-Cituwous It; Web<r, E.; Bishop, R., Eds.; T()Clics in Cum:nt Chearislry 149;
Sprillp'-V..taa; lktlin, 1,...
EHects of Chemical Forces
Effects of
Chemical
Forces
Melting and Boiling
Paints
307
Fusion and vaporization result from supplying sufficient thermal energy to a crystal to
overcome the potential energy holding it together. II should be noted that in most
cases the melting and vaporization or a crystal does not result in atomilOtion, that is,
the complete breaking or all chemical forces. In order to understand the relationship
between chemical forces and physical properties such as melting and boiling pointS, it
is necessary to compare the binding energies of the species in the vapor with those in
the crystal. Only the difference between these two energies must be supplied in order
to vaporize the solid. The following discussion will emphasize energy differences with
respect to variation in melting and boiling points. but it should be realized that entropy
effects can also be very important.
Crystals held together solely by London dispersion forces melt at comparatively
low temperatures and the resulting liquids vaporize eusily. Examples of this type are
the noble gases which boil at temperatures ranging from - 269 OC (He) to -62 c (Rn).
Many organic and inorganic molecules with zero dipole moments such as CH. (bp
-162 c>. BF3 (bp = - tOI c>. and SF6 (sublimes at - 64 c> fall into this category.
Because London forces increase greatly with polarizability, many larger molecules
Conn liquids or even solids at room temperature despite having only this type or
attraction between molecules. Examples are Ni(COJ. (bp "' 43 "C), C04 (bp =
17 "C), borazine. B3N 3 H6 (bp S3 "C), and trimeric phosphazene, P3N3CI6 (mp c
114 "C).
It should be noted that these compounds are a trivial illustration or the principle
stated in the first paragraph. Although all of the molecules contain very strong
covalrnt bonds, none is broken on melting or vaporization, and hence they play no
part in determining the melting :1nd boiling pointS.
The melting point or a compound is anot her property to which symmetry is an
important contributor. Symmetrical molecules tend to have higher melting points
than their less symmetrical isomers. For example, the melting point oC neopentane is
- 17 c. that of n-pentane - 130 c. If the molecule has very high symmetry, the
melting point may be raised until the substance sublimes rather than melts. lf you
think about some substance that you know sublimes (in addition to SF6 mentioned
above), yo u will note that it has high symmetry. Common examples are 12, C02, and
camphor. The extreme example is perhaps dodecahedrane, C 20H2n=
It has a mp of 430
10 c.
to obtain because of sublimation. This is about
100 c higher than the bp of the straight chain hydrocarbon of similar molecular
weight. n-eicosane (bp = 343 c), and almost 400 c higher than its mp (37 "C). The
difference lies in the high symmetry(/,.) oC dodecahedrane. As the temperature rises,
the molecules can pick up energy in the form of rotations. and even diffusion (translation), without disrupting the lattice and forcing meltina to occur.
Molecules in polar liquids such as water. liquid ammonia, sulfuric acid, and
chloroform are held together by dipole-dipole and hydrogen bonding interactions. For
molecules oC comparable size, these are stronger than London forces resufting in the
familiar trends in boiling points nonmet al .h ydrides. For the heavier molecules, such
as HzS, HzSe, PH 3 , and HI. dipole effects are not particularly impor1ant (the elec-
or
308
8 O..onical FO<c:es
lronegativities of the nonmetals are very similar to that of hydrogen} and the boili11g
points are low and increase with increasing molecular weight. The first membe.r of
each series (H20. NH), HF) is strongly hydrogen bonded in the liquid state and has a
higher boili!1g point .
Ionic compounds are characterized by very strong electrostatic forces holding the
ions together. Vaporization results in ion pairs and other small clusters in the vapor
phase. Although the stabilizing ene.rgies of these spec.ies are large, they are considerably less than those of the crystals. Assuming u hard-sphere model as a first approximation, the difference in electrostatic e.ne.rgies of an ion pair in the gas and the solid
lattice would lie in their Madelung constants. For Naf. A = 1.00 for an ion pair, I.75
for the lattice. We should thus expect that if crystalline sodium fluoride vaporized to
form ion pairs, the bond energy would be slightly more than half(I.00/1.75 = 0.57) of
the lallice ene.rgy. There are several factors that help stabilize the species in the gas
phase and make their fonnation somewhat less costly. Polarization can occur more
readily in a single ion pair than in the lattice. This results in a somewhat greater
covale.nt contribution and shorter bond distances in the gas phase. Secondly. in
addition to ion pairs there are small clusters of ions with a greater number of
interactions and more auractive energy. It is not surprising to learn. therefore. t hat
vaporization costs only about one-fourth of the lattice energy. not almost one-half
(Table 8.5). Nevertheless. since lattice energies are large. the energy necessary to
vaporize an ionic compound is large and responsible for the high boiling points of ionic
compounds.
Table 8.S
Dissocia!N>n -sie of the

alkali hcolid.n fw 11>. salicl
one! gas phases (ltl mol- ')
+ x-(g)
C-.-mel
MX(g)-M (g)
LiF
UCl
IJBr
1M
636
615
Lil
573
NaF
NaO
NaBr
Nal
KF
KO
KBr
Kl
Rbf
RbO
RbBr
Rbl
CsF
csa
CsBr
Csl
644
799
741
916
506
.582
494
741
690
812
707
556
536
MX(s}-M (g)
1033
845
ns
678
448
565
640
498
686
464
661
623
749
653
632
602
439
S48
464
448
414
ns
+ x - (g)
E,..,
268
209
184
167
222
205
184
230
213
201
192
213
188
197
184
201
197
184
188
Ratio
0.26
0.25
0.23
0.23
0.30
0.28
0.28
0.27
0.29
0.30
0.30
0.30
0.27
0.27
0.30
0.30
0.27
0.29
0.29
0.31
Gaspluose data are from the bond enerzies in Appendix E corrected to the ionic
case by addition or lhe loftizalion enetJY and electron IIIT'onily. Lartice ene1Jies are
from tbe best values in nble 4.3. Enerzjes ol sublimatioa (assumins ion pairing) are
lhe clilfer<nee bdween the enetaY or the latlice and that or the ion pairs. The ratio ia
yidcls the fraction or the ei!Cfly "lose oc sublimatlaa.
J
Increasing the ionic charges wiR certainly increase the laltice energy o{ a crystal.
For compounds which are predominantly ionic, increased ionic charges will result in
increased melting and boiling points. Examples are NaF. mp 997 'C, and Mg0,
mp = 2800"C.
The situation is not always so simple as in the comparison of sodium ftuoride and
magnesium oxide. Accordil18 to Fl\ians' rules. increasing charge results in increasing
covalency, especially for small cations and large anions. Covalency per se does not
necessarily favor either high or low melting and boiling points. For species which are
stroi181Y covalcnlly bonded in the solid, but have weaker or fewer covalent bonds in
the gas phase, melting and boiling points can be extremely high . Examples are carbon
in the diamond and graphite forms (sublimes about 3700 'C) and silicon dioxide (me.lts
at 1710 c. boils above 2200 c). For example, in the latter compound t.he transition
consists o{ changing four strong tetrahedral u bonds in the solid polymer to two o-and
two relatively weak .,. bonds in the isolated gas molecules:
1:8.18)
On the othu hand, if the covaleO( bonds are almost as stable and as oomerous in the
glls-phase molecules as in the solid, vaporiz.:llion takes place readily. Examples are the
depolymerization reactions that take place at a few hundred dqrees. For eJCample, red
phosphorus sublimes and recondenses as white phosphorus.lS
/P'-.
/p'-.
'-p/
'-p/
I P- P I
-+
II
2n
/p'-.
PI-P
'-p /
(8.19)
Thus increased covalent bonding resulting from Fajans-type phenomena can !o ... the
transition temperalures. For example, the alkali halides (except CsCI, CsBr, and CSI)
and the silver halides (except Agl) crystallize in the NaO structure. The sizes o{ the
cations are comparable: Na = 116 pm. Ag 129 pm, K+ "' IS2 pm, yet the
melting points of the halides are considerably different (Table 8.6). The greater
covalent character o{ the silver halide bond (resulting ftom the diO electron configuration) compared with those in the alkali halides helps stabilize discrete AgX molecules
in the liquid and thus makes the melting points of the silver compounds lower than
those of the potassium compounds. A similar comparison can be made between the
TollleU
KF"' 858 'C

J<Os770"C
KBr,. 734 "C
AgF,. 43S "C

Agel"' 4.SS "C
A&Br - 432 c
NaF 993 'C

NaO 801 "C
NaBr 747 "C
is unl<nown. but this SlNCtiiR W been

II'&!Jrnenl here Is 1101 dependent on knowledce ol the exace strUCture.
U Tbe UXl 111\lCtUtC o( red
The
310
8 Chemical fatces
Tobit 8.7
2
7J.C
CsF = 682
KBr
CaBr2
BaF2
730
13.55
KBr 143$
Csf 12SI
CaBr1 = 812
Bafl .. 2137
predominantly ionic species CsF and Baf2 and the more covalent species KBr and
CaBr,(Table 8.7). The change from l : l to 1:2 composition in the highly ionic ftuorides
prod.;ces the expected increase in lattice energy and corresponding increase in the
transition temperatures. For the more covalent bromides, however. the molecular
species CaBr2 (in the gas phase and possibly to some extent in the liquid) has sufficient
stability via it.s covalency so that the meltins point is about the same as that of KBr,
and the boilins point is actually lower.
In extreme cases of Fajans' effects, as in Bel2 and transition metal bromides and
iodides. the stabilization resultins from covalency is very large. Distortion of the
lattice occurs and direct comparison with ionic halides is difficult . For metal halides
the boilins points of these compounds are comparatively low as expected: Bel, =
S90 c. Znl2 .. 624 c. FeCI3 31 S c. The extreme of this trend is for the covaient
forces to become so strons as to define discrete molecules even in the solid (e.g .
AI2Br6 mp 2 97 "C. bp - 263 "C). At this point we have come full circle and are back
at the SF6 and C04 situation.
Solu b ility
Solubility and the behavior of solutes is a complicated subject,Z6 and only a brief
0\ltline will be siven here. A further discussion of solutions will be found in
Chapter 10.
Solutions of nonpolar solutes in nonpolar solvents represent the simplest type .
The forces involved in solute-solvent and solvent- solvent interactions are all London
dispersion forces and relatively weak. The presence of these forces resulting in a
condensed phase is the only difference from the mixing of ideal gases. As in the latter
case. the only drivins force is the entropy (randomness} ofmixins. In an ideal solution
(OJI..w.. - 0} at constant temperature the free energy chanse will be composed
solely of the entropy term:
t..c = t..H- ns
(8.20}
f>.G = -TAS
(8.21)
(for f>.H =OJ
The change in entropy for the formation of a solution of this Jype is:7
AS = - R<n, In x,. + n8 In xu)
x,.
(8.22)
where
and x8 are the mole frac.t ions of solute and solvent. For an equimolar
mixture of "solute" and "solvent " the change in free energy upon solution at room
temperat ure is rather small, only - I.7 kJ mol- 1
2o For more detailed discussions of soMe bdlavior. see Hildebrand. J. H.; Scott, R. L. 1}, SoiMhility
o/Non.ntrolyus; v., Nostrand-Reinhold: New Yort. 1950; Rc>binson; R. A.; Stokes, R. H.
Ekctrolytr Solutio"s 2nd ed.; BUUerworlhs: London. 19l9.
2'7 For the oriai o( tllis CJtprcsoion ...d an aoeknt ciKussion o( the thormodynamks o( solution
formation. s Barrow. G. Pllysit:a/ Ch,misll')', 4th eel. ; Mc<inlw-HiR: New Yort. 1979.
At the other extreme from the ideal solutions of nonpolar substances are solutions
of ionic compounds in a very polar solvent such as water. The entropy change for such
a process may be positive or neptive unlike in the ideal solute- solvent interaction
described above. In addition to the increased disorder expected as ions go from solid
to solution, there will also be an ordering of solvent molecules as these ions become
solvated. The positive tenn will be dominant for large ions of low charge, but for ions
that interact strongly with water (small si:te and high charge), the nesative tenn
becomes more important. For many salts the entropy contribution to the free energy
change for dissolution is comparable in magnitude to the enthalpy change and both
terms must be considered.Z
In order for an ionic compound to dissolve, the Madelung energy or electrostatic
attraction between the ions in the lattice must be overcome. In a solution in which
the ions are separated by molecules of a solvent with a high dielectric constant
(e-H,o
81. 7o) the attractive force will be considerably less. The process of solution
of an ionic compound in water may be considered by a Bom- Haber type of cycle. The
over.tll enthalpy of the process is the sum of two terms , the enthalpy of dissociating
the ions from the lattice (the lattice energy) and the enthalpy of introducing the
dissociated ions into the solvent (the solvation energy):
-1
xw
XW
(8.2.3)
M(H20 ); + X(H 2
0);
Two factors will contribute to the magnitude of the enthalpy of solvat.i on. One is the
inherent ability of the solvent to coordinate strongly to the ions involved. Polar
solvents are able to coordinate well through the attraction of the solvent dipole to the
solute ions. The second factor is the type of ion involved, particularly its size. The
strength and number of interactions between sol vent molecules and an ion will depend
upon how large the latter is. The lattice energy of the solute also depends upon ionic
si:te. The forces in the lauice are inherently stronger (ion-ion) than those holdir the
solvent molecules to the ion (ion-dipole), but there are several of the latter interactions for each ion. As u result. the enthalpy of solvation is roughly of the same order of
magnitude as the lattice enthalpy, nnd so the total enthalpy ot solution can be either
positive or negative dependina upon the particular compound. When the enthalpy of
solution is negative and the entropy of solution is positive, the free energy of solution
is especially favorable since then the enthalpy and entropy of solution reinforce each
other.
In many cases the enthalpy of solution fo r ionic compounds in water is positive. In
these cases we find the solution cooling as the solute dissolves. The mixing tendency
of entropy is fordng the solution to do work to pull the ions apart, and since in an
adiabatic process such work can be done only at the expense of internal energy , the
solution cools. If the enthalpy of solution is sufficiently positive, favorable entropy
may not be able to overcome it and the compound will be insoluble. Thus some ionic
compounds. such as KC104 , are essentially insoluble in water at room temperature.
The fact that the solubility of a salt depends critically upon the enthalpy of
solution raises an interesting question concerniclg the magnitude of this quantity.
:zo Cox. B. G .; Parlter. A. J . J. CMm. $. 19'73. 9.S,
312
I Chemic:al Forces
Obviously, a large $01vation enthalpy contributes toward a favorable enthalpy o(

solution. However, we lind that the solvation enthalpy alone provides us with
liule predictive usefulness. Water soluble salts are known with both large (Cal,,
-2180 kJ mol- 1) and small (KI, - 61 1 kJ mol- 1) hydration energies; insoluble saris
are also known with large (CaF, -6782 kJ mol- 1) or sn\8.11 (LiF. - 1004 kJ mol- 1)
hydration energies. ll is appare;t that the hydration e.nergies alone do nol determine
the solubility. Countering the hydration energies in these cases is the Jauice energy.
Both Janice energy and hydration e.nergy (Fig. 4.20) are favored by large charge (Z)
and small size (r). The difference lies in the nature of the dependence upon distance.
equation for the lattice energy (Eq. 4. 13) may be wriuen as a
The
function o( distance:
1
U=/1 ( -- )
' +r_
(8.24)
The simplest equation for the enlha.lpies of hydration of the cation and anion (Eq. 4.27)
may be rewriuen as:
(8.25)
Now the luttiu energy is inversely proportional to the sum of the radii, whereas the
hydration enthalpy is the sum of twO qut1ntities inversely proportional to the individwa/
radii.. Oearfy the two functions will respond differently to variation in r .. and r -
Without delving into the details o( the calculations, we Rl8y note that Eq . 8.24 is
favored relative to Eq. 8.25 when r r _ and the reverse is true for r _ << r.. or
r_ >> r ... To express it in terms o( a physical picture, the Jauice energy is favored
when the ions arc similar in size- the presence o( either a much larger cation or a
much larger anion can effectively reduce it. In contrast, the hydration enthalpy is the
sum of the two individual ion enthalpies, and if just one of these is very large (from a
sincle, small ion), the lotal Rl8Y still be sizable even if the counterion is unfavorable
(because it is large). The effects of this principle may be seen from the solubilitY of the
alkali halides in water. Lithium fluoride is simultaneously the least soluble lithium
halide and t he least soluble alkali fluoride. Cesium iodide is the least soluble cesium
halide and the least soluble alkali iodide. The most soluble salts in the series are those
with the most disparate sizes, cesium fluoride and lithium iodide.29
The enthalpy of solution has been discussed somewhat more quantitatively by
Monis.lO He has pointed out the relation between the enthalpy o( solution and the
difference between the hydration enthalpy of the calion and that of the anion. This
difference will be largest when the cation and anion differ most in size (Fig. 8.9). In
these cases the enthalpy of solution tends to be large and negative and favors solution.
When the hydration enthalpies (and the sizes) are more nearly alike, the crystal is
favored. When entropy effects are added, a very nice correlation with the solubility
lltld the free energy solution is found (Fig. 8. 10).
There is a very practical consequence of the relation of solubility to size. It is
often possible to make a large, complex ion from a metal and several ligands that is
stable in solution but difficult to isolate without decomposition . Isolation of such
a very thornuch disrus.Yon of enlhalpy,
and the aolubilily of
see
.ldtnson. D. A. So""'
Asptct o/lltO'fOI'Ic Clo,Utry; Cambridce Urivusity:
Londoo. t968. Chapter 5.
JO Morris. D. F. C. Stnlct. BoNiitrg (Bnlilll 1968, 4, 63: ,,.,, 6, t57.
l t For
Effeds of a.. ...ical Forces
313
f1g. 8.9 Relation between

tile heat of soiUJion or a salt
Md Ute individual heats or
hydration o( the component
ions. (From Monis, D. F. C.
Suurl. Bonditlg (Berlin)
1969, 6. lS1. Reproduced
with permission.!
...
c
.!!
-;
-!0
Fag. 8.10 Relation betwc<n

the free enersy of solution
d a salt and the individual
+20
free enerzjes of hydration

d the component ions.
lFrom Manis. D. F. C.
Strurt. Bonding (B,rlin)
1969, 6, tS1. Reproduced
with permission.)
OUI
-200
-tOO
Oilfermcc in
+100
+200
1n.v.1
and cation (U mor 1 l
large complex ions is

by attempting to precipitate them as salts of equaRy
large counterions. This favors the stability of the crystalline state rdative to solution and makes it easier to obtain crystals of the desired complex. For eX8q)le,
the [Ni(CN)sl,_ ion was known to exist in solution but when solutions were
evaporated, even in the presence of saturated KCN. only
could
be isolated. However, addition of large complex ions of chromium such as hexaamminechromium(lll). (Cr{NH,)J)+, and tris(ethylenediamine)chromium(lll),
(Cr{NH2CH2CH2 NH1 ),)J+, aUows Jhe sep3t'3tion of (Cr{NH,)J[Ni(CN)5 )2H10 and
314
8 Ch emical Forces
both eX which are stoble at room temperature.)'

The insolubility oC ionic compounds in nonpolar solvents is a similar phenomenon. The solvation energies are limited to those from ion-induced dipole forces.
which are considerably weaker than ion-dipole forces and not large enough to overcome the very strong ion-ion forces eX the lattice.
The reason for the insolubility oC nonpolar solutes in some polar solvents such as
water is less apJ)IIrent. T he forces holding the solute molecules to each other (i.e .. the
forces tending to keep the crystal from dissolving) are very weak London forces. The
interactions between wuter and the solute (dipole - induced dipole) are also weak but
expected to be somewhat stronger than London forces. It might be supposed that this
small solvation energy plus the entropy of mixing would be sufficient to cause a
nonpolar solute to dissolve. In fact. it does not
any entropy resulting from the
disordering of the hydrogen bonded structure eX the solvent water is more than offset
by the loss of energy from the breaking oC hydrogen bonds. Anthropomorphically we
might say that the solute would willingly dissolve but that t he Wolter would rather
associate with itself.
We can summarize the energetics of solution as follows. There will usually be an
entropy drivi'l: force favoring solution. In cases where the enthalpy is negative. zero,
or slightly positive. solution wiD take pfllce. If the enthalpy change accompanying
soiU(ion is too positive. solution will not occur. In qualitatively estimating the en.
thalpy effect. solute-solute, solvent-solvent. and solute-11olvel1( interactions must be
considered:
AH...,Iut;.,., = AH...,Iutc-'<d.vm -
AH-olvcrw-1<4lvcm
(8.26)
where the various energies result from ion- ion. ion-dipole. ion-induced dipole.
dipole-dipole. and London forces.
Problems
8..1
from fig. B. I describe the crystal structure or solid UfliOR.
11.2 Confirm the Slutement made on p:tJ!t :!')()

the von der W;tol' nodi us o( araon is 190 pm,
usins fig . 8.1 nd the
thut the unit cell is S3S pm on
Predict the internuclear

in the fllllowina mok:cules and l;u ticcs by usc or the
oppropriute vnn tier Wuuls. ionic. covalent . unci a tomic r.J<Jii. In those cases where two or
more
t)( values are applicable . determine whidl yield tile results closest to the
cxperimentul vulll<!s,
System
Dist_,.
Uf molecule
LiF crystnl
Csl molecule
Csl crystal
Ul molecule
l..il crystal
Xef4 molecule
Xef4 crystnl
H,O molecule
s.la. molecule
L.i- f
ISS
Li-f
Cs- 1
Cs-1
201
332
39S
Li-1
L.i-1
239
Xe-f
f - f !different molecules!
H--()
Sn-0
r(pm)
194
313
96
233
" for diSOisrion of this subject. sec kwlo. F. CH>rd. Clvm. Rn. l96J. J. 21); Mincos- D. M. P.;
Rolf. A. L. ln"'1/.
1991. JIJ. 3769-Jnt.
Problems
31 S
or
8.4 At one time the melting points of the fluorides

the third-row elemcn1s were taken to
indicate a discontinuity between ionic bonding (AIF,) and covalent bondil"4! (SiF4 ). Explain
1he observed trend assuming that the bond polarity decreases uniformly from NaF to SF
NaF 993
MgF1
1261 'C
AIF, 1291 'C
PF, = -83 'C
SiF"' - 90 'C
SF = -S I
'C
8.5 List the foUowing in order or increasing boiling point:
H10
Xe
LiF
L..il
BnO
SiCS.
SiO,
8.6 The majorily
c:ompotmds involve hydrogen bonding in the hosl cages. Discuss

how the intermediate nature of the hydrogen bond (i.e ., stronger than van der Waals
forces, weaker than ionic forces) is relaled to the prevalence of hydrogen bonded
clathrates.
8.7 Two forms of boron nitride are known. Tile ordinary form is a slippery while matmal. The
second. formed artificially at hiah pressures. is the second hardest substance known. Both
remain as solids at temperatures appcoaching 3000 'C. SuggeSt structures.
8.8 Predict bond lengths in the following: H 20. HO. NF,. CF,, H,S. SF,.
8.9 Tile Schomakcr-Stcvenson relationship states that heteropolar bonds arc always stronger
and shon..- !han hypothetical. purely covalent bonds between the same atoms. In an ionic
crystal, would you expec1 some covalency to Shonen or lengthen 1he bond? ExpiDin.
(Shannon. R. D. ; Vincent. H. Suuct. BondinJI (B,Iin) 1914. /9, 1.)
8.10 Find the melling poinls and boiling points of the elcmen1s or compound.< listed. For each
series. tabulate the data and explain the trends you observe In terms of I he forces involved:
a. He, Ne, Ar. Kr. Xe

b. H,O, H,S. H,SC. H2Te
c. CH,, CH,O. CH,O,, CHO,, CO.
d. Carbon. nitrogen. oxygen. fluorine. neon
8.11 Consider the sizes of the iSOekctronic species N" - . o>-. F"". and Ne. Discus.< the forces
operatina. C<wf'at! Be careful in chooloing which numbers to
in your discus.<ion.
1
8.12 Tile s!Jibilil)f or noble gas configurations was di.<eussed in Chap1cr 4, where it was pointed
out thai many ions arc not Slablc. that is, they are endolhermic with respect to the
corresponding atoms. but they are slabilized by the ionic: lattice. However. some chemists
st3ble becnu,..they
in olution well in luuiccs. Discuss.
argue I hat these ions
8.13 Consider 1hc ions
and (Ph,P= N=PPh,l.
a . Work out 1he electronic structures of 1hese ions in detail including assigning formal
charges.
b. Compare the geometries and other similarities or difference,;.
c. How should these ions prove useful in inorganic synthesis?
8. 14 Water i.s wei known 10 have an unusuaDy high heat capncity. Not so well known is that
liquid XeF6 also has a high heal capacity compared to "normal" liquids such as arson.
carbon tetrachloride, or sulfur dioxide. From your knowledge of the strucluresofthe!IO!ids
and the sascous molecules of 1hese materials (most of them are skctc.h ed in this text),
explain the "anomalous" heat capacity of XeF .
8.15 Find the solubilities In water of the alkali halides. Calculate the molarity or moluli1y las
convenient) of a saturated SOlution fur cnch and plol them in matrix form with columns
headed F. 0, Br. I, and horizon1a1 rows labeled L..i. Na, K, Rb, and Cs. Di.cuss any trends
you notice.
8.16 In these fi.-.t eight chapte.-. you have encountered many tables of atomic and molecular
316
8 Che mical f orces
properties. They may be cla$Sifoed in10 lwo aroups: 1I l raolial wave functions. ioniz:uion
en..-gies. clec1roo affinilics. etc. ; (2) ionic radii. covale:nl rndii , clcclroncsatillities, etc.
a. What dislinguish<s and separ.>tcs
two groups?
b. Lee Allen lpers. comm.) has suuested thai it is the probkm.<associated with I he second
group that make chemistry a distinct and interectins science. not jusl a sub-branch of
chemical pllysics.
8.17 Predic.l which of the followina bondinc interactions wiU be lhe stronger:
a. 0=0 or 0-0
b. C-C or Si-Si
c. Ne-Ne or Xe- Xc
d. Li F - or
c. uF- or
r.
(ion puir)
(ion pt<irl
uF- or C- C lin uiumond)
8.111 Predict the follOwing bond len&lhs:
c-o (ketones}
C-O (earboo monol<iclcl
s. double in (HOl,P-OJ
C-N (cyaniclcl
P-0 (sin&)c
N-0 (nitric oxide)
N-0 (nitroaen dioxide)
Compare your answers with lhe values &ive:n in Table E. I, Appendix E.
8.19 Reconsider Problem 4. tS. Extend your cxpbnation: Susgcst a means of sl:lbilizinQ hen
lluoropialinaJt( V) sahs.
8.20 How will the IR and Ramon spectra of FHJ"" and CIH r
8.21 On pase .l02 il was Shted lhat allhoush l he FHF" anion was II.SUOI.Dy symmelrical . occasionliiJy il was found to be unsymmetrical in the SCllid. What pllysialmelllods could you
usc 10 delcct unsymmetrical FHF- ions in a >Oiid?
8.22 If you did not do Problems 4.37 and 4.38 when you
Chapter 4. do them now.
8.23 In Ihe preparation orthc bisiNnilrosopyrrolidine)hydrQicn cation with the shot1 hydrogen
bond (Fig. 8.5). the compkox wa5 made by
a SOlution of N nil rosopyrrOiidi ne
and hexalluor ophosplloric acid in ether to obtain crystals. Why hexalluorophosphoric acid?
Why not hydroi\Joric ""id?
8.24 If you did no1 do Problem 6. 1S when you read Chapter 6, do it now.
8.25 How would you characterize lhe hydrogen bond described in Problem 3.42?
8.26 The ammonium ion is about I he
l r. IS I pml as the po1ussium ion (r. ,.
JS2 pm) and I his is a useful fac110 remember when
rcscmbbnce in propenics
beawecn these two ions. For example. the solubilities of 3mmonium snits are similar 10
of potassium
Explain the relation between ionic radius and solubility. On the
other hand, aU of the potaS$ium halides cryslallizc in the NaO Slruclure wilh C .N. 6 (sec
Chapter 4). but tttJflf' of the ammonium halides docs so. The coordination numbers the
ammonium halides are either four or ei&hl. Sucsest an explanation.
8.27 Find as many data as you can (distances. cncr&ies, etc.) on hydrogen bonds and hydrogen
bridses. Use I his chapter. Cha,pten IS and 16. and any other sources. Arrange the data and
arsue (hOwever you concludeI thai hydroaen
such as F- H- F and hydrogen
bridges sucfl as W-H-W (are. are noel rncrdy 1he e nd o f a continuous spectrum of
bond ing. (Sec B:au. R.: TeDer, R. 0 .: Ki t1ley, S . W.; KoetzJe. T . F. Ace. Clrmr.
1979,
12. 176-183.)
11.28 If you d id not do Problem J.34 w11en you rta.l Chapt..- 3. do it now.
8..29 The clas$ical qualilativc analysis scheme is
and c:Norides (except for Ag .
based on solubility rules: Acetates, nitrates.
Hai. and Pb1 ) are always SOluble. There arc spc<:ilic:
sOlubility pallemS I wllidcs. c:ubonates. and pftosphales. Find a qual scheme and
explain it in 1erms of yoor IMiderstanding of so.,tion processes.
Proble111s
317
8.30 The pOint is made e:ltty in this

lhal compaNons ofatomic ndii should be resJricted
to lhe Slltne type of r:Miii: van cler
vs. van cler Waal. cowtent vs. covalent. etc. In
class one day a studen1 asked ... Which is lllt.:er. the van der Waals radius of neon or 1he
ion? DiSCIJSll .
covalent radius of sodium'!"" I!) Was Ihat a nonsensiul
8.31 Superimpose Figs. 8.:! and 8.3 (a b. but not bolh at the same lime). Discuss 1he physical
picture of van der Waals, ionic , unll covalent radii and the problems nssocin1ed wilh the
calculations on paae :!93 .
C h a p
e r
9
Acid-Bose Chemistry
Acids and bases are fundamental to inorganic chemistry. Together with the closely
refated subjects ofredox and coordination chemistry. they form the basis of descriptive inorganic chemistry. Because they
so fUndamental, there has been much work
(and sometimes much disagreement) attempting to lind the "best" way of treating the
subject.
Acid-Bose
Concepts
The first point to be made concerninG acids lind bases is thot so-called acid-base
"theories.. are in reality d<ifinitiom of what an acid or base is; they are not theories in
the sense of valence bond theory or molecular orbital theory. In a very real sense. we
can make an acid be anything we wish; the differences between the various acid-base
concepts are not concerned with which is "risht" but which is most convenient to use
in a partic11lur si/1/ation. All of the current definitions of acid-base behavior are
compatible with each other. In fact , one of the objects in the following prese.n tation of
many different definitions is 10 emphasize their basic parallelism and hence to direct
the students toward " cosmopolitan atlitude toward acids and bases which will stand
them in good stead in dealing with various chemical situations. whether they be in
aqueous solutions of ions. organic reactions. nonaqueous titrations. or other
situations.
Brvnsted-Lowry
In 1923 J . N . B!llnsled and T. M. Lowry independently suggested that acids M

defined as protonZ donors and baus as proton
For aqueous solutions the
De(,nition
BrllnSied, J . N . Rrd. Trn. C/lim. Pays&JJ lfZJ, 42. 718-728; Lowry. T . M. CMm. /ltd. (l.om/on)
1913, 42, 43.
As this book was coi"K to press the lntcrnllicnal Union ol Plft a.ocl Applied Chemistry recommended that the won! prt>1011 be
only when the 'H isotope was !mended, and that the more
acnu:al lrydrae be used e.aywhere
as in
IIOIIOf'. See Appendix 1. Scetion 8. We hove not
atlemJlled at the ta.st minute to c:bal1&e aU ol the.sc "prolons'' to " hyclrons. Lilce the Sl system or
unils. this c:flal1&e, it accc:pted by the world's dlomisu. will Jake some time. and Jhc tmn "pn:ilon
donor" will not soon disappear.
"*
318
Acid-Base c-cepts
3 19
definition does not differ appreciably from the Arrhenius definition
of hydrogen ions (acids) and hydroxide ions (bases):
2H20
H30 + + OH-
(9.1)
Pure SOIYc.nl
The usefulness of the

definition lies in its ability to handle any
protonic solvent such as liquid ammonia or sulfuric acid:
NH! + NH:!--+
Acid
Base
so:
H3
2NH 3
+ HS04 -
Acid
(9.2)
Ncutntiwion
proWcl
Base
so.
2H 2
(9.3)
Neulr.llizalion
producl
In addition, other proton-transfer reactions that would not normally be called oeutialization reactions but which are obviously acid-base in character may be treated as
readily:
(9.4)
Chemical species that differ from each other only to the extent ol the transferred
proton are termed conjugatu (connected by brackets in Eq. 9.4). Reactions such as
the above proceed in the direc1ion of forming weaker species. The stroni!Cr acid and
the stronger base of each conjuaate pair react to form the weaker acid and base. The
definition places on competition for protons is
emphasis which the
one of the assets of working in this context , but it also limits the fiexibility ol the
coocep. However. as long as one is dealing with a protonic solvent system. the
definition is as useful as any. The acid-base definitions given below
were formulated in an attempt to extend
concepts to systems not containing
protons.
lux-Flood Definition
In contrast to the Brpnsted-Lowry theory, which emphasizes the proton as the

principal species in acid-base reactions, the definition proposed by Lux and extended
by flood3 describes acid-base behavior in terms of the oxide ion. This acid-base
concept was advanced to treat nonprotonic systems which were not amenable to the
Brpnsted-Lowry definition. For example, in high-temperature inorganic melts. reactions such as the following take place:
CaO
+ Si01
....
Acid
- + CnSi01
Lux. H. Z. DduocMm. 19, 41.303. Rood. H.: FCirtlnd. T. Actu Ch-. &ttttJ.
781. Flood, H.: FOUad. T.; Roald, B. Ibid.
I,
(9.5)
S92-()()4,
Tile base (Ca0) is an oxidt! donor and the acid (Si02 ) is an oxidt! acct!ptor. The
userulness of the Lux-Flood definition is mostly limited to systems such as mollen
oxides.
This approach emphasizes the acid- and basic-anhydride aspects of acid-base
chemistry, certainly useful though often neglected. The Lux- Flood base is a basic
anhydride:
Ca2+
+0
1-
+ H 20
- - + Cal+
+ 20H -
(9.6)
and the Lux- Flood acid is an acid anhydride:

Si01 + H 2 0 -
H 2 Si0,
(9.1)
(This Iauer reaction is very slow as written and is of more importance in the reverse.
dehydration reaction.) The c haracterization of these metal and nonmetal oxides as
acids and bases is of help in rationalizins the workings, for example, of a basic
Bessemer convener in steelmaking. The identification or these acidic and basic
species will also prove useful in developing a general definition of acid-base behavior.
An acidity scale has been proposed in which the difference in the acidity parameters, (a 8 - aA) of a metlll oxide and a nonmetal oxide is the square root of the
enthalpy of reaction of the acid and base. Thus for reaction 9.S. the enthalpy of
reaction is - 86 kJ mol- 1 and so the a values ofCaO and Si02 differ by about 9 units.
Selected values are listed in Table 9. 1. Although based on the Lux-Flood concept, the
values are obviously or more aeneral interest. The most basic oxide, as expected, is
cesium oxide, amphoteric oxides have values near zero (water was chosen to calibrate
the scale at a value of 0.0). and the most acidic oxide is Cl20 7 the anhydride of
pe.rchloric acid.
Tile decomposition of carbonates and su)(ates discussed previously (Chapter 4)
can be viewed as the tendency of metal cations to behave u oxide ion acceptors
(Lux-Flood acids), and the ordering shown in Fis. 4.2 1 can be related to measures of
acid-base behavior or these metals (e. a. cf. Table 9.3). The nonexistence of iron(lll)
carbonate, for example. in Fig. 4.21 indicates that the FeH ion is too strons an acid to
aUow it to coexist with carbonate: or in tenns of the a parameter above, the enthalpy
of reaction to form iron( III) caltonate is expected to be only about - (- 1.7 - S.S)1 or
about -52 kJ mol- 1, not enough to overcome the Tl!.S term of the free enersy change,
arisins larse.ly because or gaseous carbon dioxide:
(9.8)
Solvent System
Definition
Many solvents autoiooize with the formation

does water:
2H1 0
or a cationic and an anionic species as
(9.10)
2HzSO.
H,o + OHNHt + NHi

H3 SOt + HSO;
20PCI,
OPCit + OPO;
(9.12)
2NH,
(9.9)
(9.11)
For the treatment of acid-base reactions, especially neutrali:talions. it is often convenient to define an acid as a 3pt!cit!3 that incuast!s lht! conCt!ntratioll of lht!
4
Smith, D. W. J . Chtm. Edu<. 1987.64, 480-41.
Acid-lose Concepts
Talole9.1
s.Mct.cl acidity para-...,
" f.,. acidic. basic:, and
.........eric: ....ides
HzO
u.o
l<zO
Rb2 0
es.,o
0.0
- 9.2
- 12.5
FeO
-3.4
CoO
- 14.6
-IS.O
Cup
NiO
- 1.7
- 3.8
- 2.4
CuO
- 1.0
- 2.5
- 15.2
-2.2
-4.S
-7.5
aeo
MgO
CaO
- 9.4
-10.8
-11.5
-6.5
-6. 1
-3.3
0.7
0.1
- 3.8
SrO
BaO
RaO
J...)l
Lu.zOJ
T.02
lllOz
VzOs
CtOJ
MC.Ol
3.0
6.6
5.2
wo3
4.7
MnO
-4.8
9.6
Tez<>.
9.6
RezO.
321
Fez01
- s.o
Ag,zO
ZnO
- 3.2
-4.4
CdO
- 3..5
1.5
HgO
8 20 1
- 2.0
5.S
0.9
6.6
9.3
7.5
Si02
N,o,
PJJoo
5.4
As,Os
so,
7. 1
IO.S
5.2
9.8
SeOz
OzO,
11.5
7.1
lzOs
9.0
VUies !'rom Smilb, D. W. J. Clttm.

due. 017, 64, 480.
charar:teristic cation of the solvent, and a base as a species that increases the
concentration of the characteristic anion. The advantages of this approach are prin
cipally those of convenience. One may treat nonaqueous solvents by analogy with
water. For example:
Kw = (Hp uoH-1 =
KAs
to- "
lAna-J
(9. 13)
(9. 14)
where [A 1 and (B-) are the concenltalions of the cationic and anio nic species
characteristic of a particular solvent. Similarly, scales analogous to the pH scale of
water may be constructed with the neutral point equal to - i log KAa although. in
practice, little work of this type has actually been done. Some examples of data of this
type for nonaqueous solvents are listed in Table 9.2. The " leveling" effect follows
quite naturally from this viewpoint. All acids and bases stronger than the c:harac
teristic cation and anion of the solvent wiD be " leveled" to the latter. Acids and bases
weaker than those of the solvent system will remain in equilibrium with them. For
example:
H 20
+ HOO. -
H,o
+ CIO;
(9.15)
322
9Acid-lose Chemistry
9.2
lon pt"OCivctJ. pH ranges,
ond ,...trol paints af some
1olv.m
lon
HzSO.
CH1 COOH
NH1
fM'O'fuct
10-
10- 13
10-
10-zo
10-29
pH .......
0-4
0-13
0-14
0-20
0-29
Neoolral point
'2
6.S
7
10
l4.S
Data from lander, 1.; l...afrenze. C. Jonltittx Soltttll; Vctlq

Chemie Gmbh: Weinhcim, 1970.
but
(9.16)
Similarfy,
NH, + Hao. ____. NHt + ao;
(9.17)
and
(9.18)
(9.19)
The solvent system concept has been used extensively as a method of classifYing
solvolysis reactions. For example, one can compare the hydrolysis of nonmetal
halides with their solvolysis by nonaqueous solvents:
+ OPCJ1
JROH + OP0 3
6NH 3 + OPCJ3
3H 2 0
+ 3HC1f
OP(OR), + 3HC1t
OP(NH:r.), + 3NH4 CI
OP(OH)j
(9.20)
(9.21)
(9.22}5
Considerable use has been made of these analogies, especially wirh reference to
nitrogen compounds and their relation to liquid ammonia as a solvent.6
One criticism of the solvent system concept is that it concentrates too heavily
of the solvent to the neon ionic: reactions in solution and on the cht mical
glect of the physical properties. For example. reactions in phosphorus oxychloride ( =
phosphoryl chloride) have been systematized in terms of the hypothetical
autoionization:
(9.23)
or
(9.24)
' Althoulh allis ...won

10 be clill'crent from the others in llloichiomctry and procllcu, the
dift'ercnce ies merely in the
basicity of
ROH. and NH 1 and the stability of their
toward dissocillloJC BH + Cl- --+ B + HCI.
Audrietll. L F.: KlcinberJ. J. fo/otwlqwo.u SoiYttllS; W'liey: New Y<t. 19D.
Acid-lose Concepts
323
Substances which increase the chloride ion concentration may be considered bases
and substances which strip chloride ion awny from the solvent with the formation of
the dichlorophosphoryl ion may be considered acids:
OPCI3 + PCI,
OPCit +PC!;
(9.25)
Extensive studies of reactions between chloride ion donors (bases) and chloride ion
acceptors (acids) have been conducted by Gutmnnn,7 who interpreted them in terms
of the above equilibria. An example is the reaction between tetramethylammonium
chloride and iron(lU) chloride, which may be carried out as a titration and followed
conductometrically:
(CH 3) 4 N+a- + FeCI 3
OI'C4
(CH 3).. NfeCI;
(9.26)
which was interpceted by Gutmann in terms of
(CH 3).&No-
OPCia
314
N+
+ Cl-
(9.27)
FeCI,+ OPCI 3 :;;:::::= OPOt +FeCI;
(9.28)
OPat +a- -
(9.29)
OPCI3
Meek and Drago8 showed that the reaction between tetramethylammonium chloride
and iron( Ill) chloride can take place just as rendily in triethyl phosphate, OP(OEt>,. as
in phosphorus oxychloride, OPCI3 They suggested that the similarities in physical
propertie.s of the t wo solvents, principally the dielectric constant. were more imptant in this reaction than the difference in chemical propenies, namely. the presence or
absence of autoionization to form chloride ions.9
One of the chief difficulties with the solvent system concept is that in the absence
of data. one is tempted to push it further than can be justified. For example, the
reaction of thionyl halides with sulfites in liquid sulfur dioxide might be supposed to
occur as follows. assuming that autoionization occurs:
2S01
..--:= SOZ+
(9.30)
Accordingly, sulfite salts may be considered bases because they increase the sulfite
ion concentration. It might then be supposed that thionyl halides behave as acids
because of d issociation to form thionyl and halide ions:
(9.31)
The reaction between cesium sulfite and thionyl chloride might now be considered to
be a neutralization reaction in which the thionyl and sulfi te ions combine to form
solvent molecules:
soz+ +so;- -
2SOz
(9.32)
Indeed, solutions of cesium sulfite and thionyl chloride in liquid sulfur dioxide yidd
the expected products:
Cs 2S0 3 + SOCI1 -
2CsCI + 2S01
(9.33)
' Gwmann, V. J. Php. Clwm. 1959,61. 171-llll. B&at. M.: Gul,.enn. V.; Hllbner, L J. lttD"' Nud.
1961, 18. 216-2:8S.
Mc:dt.D. W.; Drago. R. S. J . I\m. CJ.rm. Soc. 1961. 41, on-4125. Foracompletecliscussioncilhis
pciN of .new and ailicp>e of lhc solvCf'lt syotem :opp-OKh, see
lt. S. : l'llredl. K . F. l'r<J6.
/ncw1.
1!164, 6, 771-322.
, See Chaplcr 10 ror further clisclwion of lhia pOint.
324
9 Acicl-lat Che.,istry
Furthermore. the amphoteric behavior of the aluminum ion can be shown in sulfur
dioxide as readily as in waler. Just as AI(0H)3 is insoluble in water but dissolves
readily in either a strong acid or basic solution, AI 2(S03) 3 is insoluble in liquid sulfur
dioxide. Addition of either base (SOi- >or acid (SOh) causes the aluminum sulfite to
dissolve, and it may be reprecipitated upon neutralization.
The application of the solvent system concept to liquid sulfur dioxide chemistry
stimulated the elucidation of reactions such as those of aluminum sulfite. However.
there is no direct evidence at all for the formatiOn of S02+ in Solutions Of thionyf
halides. In fact , there is evidence to the contrary. When solutions of thionyl bromide
or thionyl chloride are prepared in "S.Iabeled (S) sulfur dioxide, almost no exchange
takes place. The half-life for the exchange is about two years or more. If ionization
took place:
2So2 ..,...:::! so2+ + s-oiSOCiz ..,...:::!
sou + 2CI-
(9.34)
(9.35)
one would expect rapid scrambling of the tagged and untaaged sulfur in the two
compounds. The lack of such a rapid exchange indicates that either EQ. 9.34 or 9.35
(or both) is incorrect.
The fact thai labeled ttuonyl bromide exchanges with thionyl chloride indicates
that perhaps the ionization shown in Eq. 9.35 actuaDy occurs aso
soa1
..,...:::!
soa +a-
<9.36)
IS.6lQ at 0 "C) the

formation of highly charged ions such as sQZ+ is energeticaUy unfavorable.
When the ionic species formed in solution are known, the solvent system approach can be useful. In solvents that are not conducive to ion formation and for
which little or nothing is known of the nature or even the existence of ions, one must
be cautious. Our familiarity with aqueous solutions of high permittivity (eH,o
81.7eo) characterized by ionic reactions tends to prejudice us toward parallels in other
solvents and thus tempts us to overextend the solvent system concept.
In a solvent with a permittivity as low as sulfur dioxide (e
l ewis Definition
In 1923 G. N. Lewis ii proposed a definition of acid- base behavior in terms of

electron-pair donation and accept:111ce. The Lewis definiti on is perhaps the most
widely used of all because of its simplicity and wide applicability, especially in the
field of organic reactions. Lewis defined a base as an
donor and an acid
as on
acceptor. In addition to all of the reactions discussed above, the
Lewis definition includes reactions in which no ions are formed and no hydrogen ions
or other ions are transferred:l2
R3N + BF3
R3NBF3
(9.37)
4CO + Ni
Ni(CO)
(9.38)
oo Ncrris, T. H. J. l'llys.
tt$9, 6J,l8l.
" Lewis, G . N.
tmd tJ"
o{Atoms DNI Moluln; Chemic:al C:ualopc: New Vorl<,
1923. Sec also Lucier, W. F.; :z.&lci, S . Tlw
fl{ AcUis DNl /kJsn, 2old rev. ed.;
Oo'o'U: New Yor\, 1961. DR"', R. S.; Matwiyotr. N. A. A<f<h tmd /kJsn; Hcalh: Lcxinlton. MA.
t968.
12
L = dectrcn .,W
such as acetone, various aminu, llalidc ion.
Adcl-llose Concepts
325
2L + SnC14
---
SnC14 l:!
t9.39J
2NH 3 + Ag
---+
Ag(NH 3){
(9.-10)
The Lewis definition thus encompasses all reactions entailing hydrogen ion. oxide ion.
or solvent interactions. as well as the formation of acid-base adducts such as R3NBF3
and all coordination compounds. Usage of the lt!wis concept is extensive in both
inorganic and organic chemistry. and so no further examples will be given here. but
many will be encountered throughout the remainder of the bouk. 13
Usanovich Definition
The Usanovich definition'4 of acids and bases has not been widely used, probably
because of ( I) the relative inaccessibility of the oriainalto non-Russian-reading chemists and (2) the awkwardness and circularity of Usanovich 's original definition. The
Usanovich definition includes all reactions of Lewis acids and bases and extends the
Iauer concept by removing the restriction that the donation or acceptance of electrons
be as shared pairs. The complete definition is as follows: An acid is any
species which reacts with basu.

up cations, or accepts anions or electrons. and,
conversely, a base is any chemical species >t1hich
with acids,
up an.ions or
electrons, or combines with cations. Although perhaps unnecessarily complicated,
this definition simply includes all Lewis acid-base reactions plus redox reactions,
which may consist ol complete transfer ol one or more electrons. Usanovich also
stressed unsaturation involved in cenain acid-base react ions:
OH-
+ O=C=O -
HOCOj
(9.41)
Unfortunately the Usanovich delinit.i on of acids a.n d bases is often dismissed

casually with the statement that it includes "almost all ol chemistry and the term
'acid-base reaction' is no longer necessary; the term reaction' is sutJicient." If some
chemical reactions were called acid-base ceactions simply to distinguish them rrom
other, non-acid-base reactions. this might be a valid criticism . However, most workers who like to talk in terms of one or more acid- base definitions do so because ol
the great systematiring power which they provide. As an example, Pearson has
shown that the inclusion of many species , even o rganic compounds not normally
considered acidic or basic, in his principle of hard and soft acids and bases he.lps the
understanding of the nature of chemical reactions (pages 344- 355). II is unfortunate
that a good deal offaddism and provincialism has been shown by chemists in this area.
As each new concept came along, it was opposed by those who felt ill at ease with the
new definitions. For eltample, when the solvent system was first proposed. some
chemists refused to call the species involved acids and bases. but insisted that they
were "acid analogues" and "base analogues"! This is semantics, not chemistry. A
similar controversy took place when the Lewis definition became widely used and
later when the Usanovich concept was popularized. Because the latter included redox
reactions, the criticism that it included too much was especiaUy vehement. That the
dividing line between electron-pair donation-acceptance (Lewis definition) and oltidation-ceduction ( Usanovich definition) is not a sharp one may be seen from the
following example. The compound C,H,NO, pyridine oxide, can be fonned by the
A very usdlll book discussi111 I'IIMIY Ojp<CIS ot

ctKmistry in 1mn1 ol II1C LewU cldinilion
is Jensea. W. B. 1M U..is Add- Bau
A" Ovctv{.-w; Wiley: New York, t980.
Usanovich. M. Ziwr. Obsclod KJ.im. 1919,9, 182. f'IIISIOn. H. L ; Ryclltman, A. C. AN- Virwof
Acid- &ur 1Mo1Ws; Wiley: New Vorl<. 1981.
IJ
326
9Acid-BoH O..mislry
oxidation of pyridine. Now this may be considered to be a Lewis adduct of pyridine

and atomic oxygen:
0 .
N : + g : - r _ N:g:
(9.4Z)
Yet no one would deny that this is a redox reaction, even though no electron transfer
has occurred between ionic species.
An example of the different points of view and different tastes in the mauer of
acid-base definitions was provided to one of the authors in graduate school while
attending lectures on acid-base chemistry from two professors. One felt that the
system was very useful, but that the Lewis concept went too far because it
included coordination chemistry. The second used Lewis concepts in all of his work.
but felt uncomfortable with the Usanovich definition because it included redox chemistry! To the latter's credit, however. he realized chat the separation was an artificial
one, and he suggested the pyridine oxide example given above.
In the prese.n ce of such a plethora of definitions . one can well ask which is the
"best" one. Each concep. proper1y used. has its strong points and its weaknesses.
One can do no beuer than to quote the concluding remarks of one of the best
discussions of acid-base concepts. u .. Actually each approach is correct as far as it
goes, and knowledge of the fundamentals of all is essential."
A Generalized
Acid- Bose Concept
One justification for discussing a large number of acid-base defitiitions, including a

few that are little used today. is to illustrate their fundamental similarity'" All define
the acid in terms of donating a positie species (a hydrogen ion or solvent cation) or
accepting a negative specit!s (an oxide ion. a pair of electrons. etc.). A base is defined
as donating a negative species (a pair of electrons, an oxide ion. a solvent anion) or
accepting a positive species (hydrogen ion). We can generali:te all these definitions by
defining acidity as a positive character of a chemical species which is decreased hy
reaction with a base; similarly basicity is a neRalie character of a chemical spt!cil!s
whkh is decreased by rt!actitJn "'ith a11 acid. The advantages of such a generalization
are twofold: (I) It incorporates the information content of the various other acid- base
defini1ions; (2) it provides a useful criterion for correlating acid-base strength with
electron density and molecular structure. Some examples may be useful in illustmting
this approach. It should be kept in mind that acid-base concepts do not <'Xpluill the
observed properties; these lie in the principles of structure and bonding.
concepts help correlate empirical observations.
I . Basicity ofmetal o.tidtts. In a given periodic group. basicity of oxides tends to
increase as one progresses down the periodic chart (see Table 9. 1). For
example. in group IIA (2) BeO is amphoteric. but the heavier oxides (MgO,
"Mocler. T. ltttlf).'OIIic Chrmistry; Wiley: New Yono. 1952: p HO. Sec :>!so Moder. T.
A Mt>J..,.n /ntN>Jucti<m; Wiley: New York. 1982; pp SIIS-603. Two other excelent
discus.ions giving different lnsiglus are: DousJas. B. E.: McD:utiet. 0 . H .: Alcxnnclu. J. J.
Conupts and MtHlth of /nmxunic Clwmhtry. 2nd ed.: Wolc:y: New York. 1983: pp St 1-SS3:
Poncrfidcl. W. W. /11orflanic Chrmistry: A Unifird Approach; Addisoo-W<Siey: Rc3di MA.
1984; pp 292-324.
1
Huheey, J. E. /nnrs:ani<: Chtmi.rtry: l'rind p/rs of Structurr

Rral'tivity: H:liJlC.r & Row: New
York. t9n: pp 21}-216. Sec also Finslon. H . L.: Ryclltman. A. C. A Nror Virw of Cu"rnt
Acid-Bou 11rrorirs: Wiley: New York. t982: C1laplcr S.
Acid-So.. Concepts
327
CaO. SrO. BaO) are basic. In this case the charge on the metal ion is the s.sme
in each species. but in the Be!+ ion it is packed into a much smaller volume,
hence its effect is more pronounced. As a result, BeO is more ac.idic and less
basic than the oxides of the larger metals. In this case. "positiveness is a
matter of the size and charge of the cation. This is closely related. of course. to
the Fajans polarizing ability (Chapter 4).
2. Acidity of nonmetal o.<ides. With increasing covalency oxides become less
basic and more acidic. Nonmetal oxides are acid anhydrides. This effect is seen
in several metal and nonmetal oxides (see Table 9.1). It can be shown that
these acidities and basicities are directly related to the electronegativities of the
metals and nonmetals involved.t7
3. Hydration and hydrolysis reactions . We have see.n (Chapters 4 and 8) that
large charge-to-size ratios for cations result in an increase in hydration energies. Close.ly related to hydration and, in fact, inseparable from it except in
degree is the phenomenon of hydrolysis. In general, we speak of hydration if
no reaction beyond simple coordination of water molecules to the cation
occurs:
(9.43)
In the case of hydrolysis reactions. the acidity (charge-to-size ratio) of the

cation is so great as to cause rupture of H-0 bonds with ionization of the
hydrate to yield hydronium ions:
Al 3+ + 6Hp -
H.O
-=..... H30 + +
(9.44)
Cations that hydrolyze extensively are those which are either small (e.g .
Bel+) or are highly charged (e.g., Fel+, Sn..) or both. and have a high chargeto-size density. Values of pKh (negative log of the hydrolysis constanl) are
compared to the (charge)Z/(size} ratiotM in Table 9.3. The correlation is good
for the main group elements and La3 but Jess so for the transition metals ,
especially the heavier ones. The reason for the apparently anomalous behavior
of metal ions such as Hg!. SnH, and PbH is not completely clear. but it may
be related to their "softness" (see page 345).
The concept of hydrolysis may also be extended to the closely related
of nonmetal halides with water:
phenomenon of the
(9.45)
In this case the water attacks and hydrolyzes not a cation but a small. highly
charged center (the trivalent phosphorus atom} resulling from the inductive
effect of the chlorine atoms.
4. Acidity of oxyacids. The strength of an oxyacid is dependent upon several
factors that relate to the inductive effect of the central atom on the hydroxyl
group: (a) The inheunt electronegativity of the central atom. Perchloric acid,
HCI04 , and nitric acid. HN03, are among the strongest acids known; sulfuric
acid, HzS04 , is only slightly weaker. In contrast, phosphoric acid, H3 P04 , and
carbonic acid, H 2C03 , are considerably weaker and boric acid. H 3B03 , is
extremely weak. (b) The inductive effect ofsubstituents. Although acetic ac.id,
CH3COOH, is rather weak, successive substitution of chlorine atoms on the
17
Bratscll, S . G. J . Clttm. Educ. 1983. 65, 877-878.

but any of1he Z/,- runctions woulcl pve
,. Z 1/rhas been used
rcsubs. SceOiaptCI'4.
328
9 Acicl-aase Chemistry
Table 9.3
pl4.
Main lf'O\IP .C.men11 Lighter transition cmcl Heavier lraMition ancl
posttramltion matalt posttransition _.als
cmcllanthonides
z2tr
2.0b
2.2
2.8
6.9
7.8
8.9
9.0
9.4
10.3
10.6
11.2
11.6
11.7
11.8
11.9
12.4
17.4
19.7
19.7
19.8
20.3
22.S
23.1
24.6
26.1
29.4
29.6
30.4
3o.6
34.2
41. 1
47.7
48.3
0 .78
0 .86
1.11
2.68
3.03
3.4.S
3.S I
3.67
4.00
4. 12
4.3S
4.52
4 .SS
4 .60
4.6S
4.82
6.78
7.68
7.69
7.73
7.89
8.78
8.99
Ag
Na 14.48
u - 13.82
Ba2 - 13.82
13. 18
sr ..
ea2
..
12.10
Mi+ "' 11.42
eez ..
c:
11.70
.1:!
::>
u
9.40
Bil+"' 1.58
uJ .. I.SO
Pu1 + = 6.9S
Lanthanides
n,. .. us
6.6
rnl .. 3.70
Scl+ Fe]+ yJ+ -
4.6
2. 19
2.92
GaJ+
3.40
4.0 1
AIJ+
.S. I4
.."'
'o
..
..8
.,..
....
!:'
eu2 Ni 1 *
.:!
;;;
10.70
10. 1
2
Co 9.6
Zn2'+ - 9.60
7.S3
Lul -
c:
0
'::1
0
Cd1 +
6.SO
La)+ .. 10.70
Increasing iendency to
rrom
Hg1 + .. 3.70
.. 7.78
- 9.51
10.2
14 ..S
li..S
11.8
11.9
13.3
16 .0
18.6
18.8
6 .9
.,e....
.1:!
....
u
..,cc:"
.
u
.:
Pu
1.6
z,A+ .. 0 .22
HI"+= 0. 12
bec8use of electronic structure
Values of pKh
Yatsimirksii. K. 8 .; Vosil'cv, V. P. lnJtobility ColllttJnts ()/Comp4u
CompotmJs; Perpmon: EJmsl'ord. NY. 1960. except for Bi, HI. Lu. Pu, Sc. and Tl, which are
from SltJbility CofUIIJIII$ of Mnal- lon
Pwt II, lnorltJnl< U6ondr. Bjcrrvm. J .;
Schwarzenbacll, G.: Sillcn, L. Ci .. Eda.; The Chemical Society: London, 19S8. For many
elcmenls 1bere is C<lruiderable unccrtalnly in the hydro!)' lis constants not only as a rcsull or
cxpcrimcnlal OI'TOf3 bUr also becauoc some haw noa been comctcd to infinite dilution. Z 2/r
values were c:akulalcd from ionic r:ldli in Table 4.4.
Acid-Base Concepts
329
methyl group increases the dissociation of the proton until trichloroacetic acid
is considerably stronger than phosphoric acid . for example.
More important for inorganic oxyacids is the number oC oxygen atoms
surrounding the central atom. Thus in the series oC chlorine oxyacids. acid
strength increases in the order HOCI < HOCIO < HOCI02 < HOCI0 3 . The
trends in ac.idity of oxyacids. and even reasonably accurate predictions of their
pK3 values, can be obtained from: Ill
pK. IO.S - S.On - X..
(9.46)
x..
for acids ofthe formula X(OH)'"O,. . and where is the electronegativity of the
central atom. Both effects (a) and (b) arc included in Eq. 9.46.
.S. Basic-ity of substit11ted amint!s.
In water, ammonia is a weak base, but nitrogen trifluoride shows no basicity whatsoever. In the NH3 molecule , the nitrogen atom is partially charged negatively from the inductive effects oC the
hydrogen atoms, but the reverse is true in the N F3 molecule. Replacement oC a
hydrogen atom in the ammonia molecule with an electron-withdrawing group
such as -OH or -NH1 also results in decreased basicity. Because alkyl
groups are normally electron donating (more so than hydrogen) toward electronegative eleme,n ts, we might expect that re.p lacement of a hydrogen atom by
a methyl group would increase the basicity of the nitroge.n atom. This effect is
readily seen in the familiar equilibrium constancs for weak bases in Water
(Table 9.4).
As expected , substitution of an alkyl group for a hydrogen atom in the
ammonia molecule results in increased electron density on the nitrogen atom
and increased basicity . Substitution of a second alkyl group also increases the
basicity. althOUBh less than miaht have been expected from the previous
substitutional effect. The trialkylamines do net continue this trend and surprisingly are as weak as or weaker than the monoalkylamines. Although the
explanation of this apparent anomaly is fairly simpl.c , it does not depend upon
electron density and so will be pos(poned to the next section.
6. "Ultimate acids and baus." Familiarity with the idea that acidity and
basicity are related to electron density at reacting sites and charge-to-size ratio
Table 9.4
8cnicity ol ammonia and Dftlines
NH1
4.74
Electron-withdrawing substitution
Less basic
Electron-donating substitution
More basic
3.36
= 3.29 Me,N 2 4.28
3.2.S 'Et1NH = 2.90
Et3N 3.2S
i-PrNH. 3.28 I-Pr1 NH - 2.9S
i-BuNH; 3.SI 1-BUzNH 2 3.32 i-Bu1N = 3..58
MeNH 1
EtNH1
19 The fnt
sudl retaliomNps were by Ricci. J. E. J. Jim.

Soc 190. 70. t09-t tJ ; Pauline. L
Clwmistry, Jnl ed.;
San Fl'3neisco, 1970; pp m.-502. The present rormulalion is
by Somaselthann. K . N .; !Ulpqam, V.
an..1(4), 43-46.
330
9 Acid- 8os Chemistry
might lead one to ask if there exists a single strongest acid or base species. A
little reflec.t ion would suggest the bare proton as having the highest positive
charge-to-size ratio. Of course the proton never occurs uncoordinated o.unsolvated in chemical systems. but attaches itself to any chemical species
containing electrons. It is too strong an acid to coexist with any base without
reacting. Even a no ble gas atom. not normally considered to be a base, will
combine with the exceedingly acidic proton (see Table 9.5). The choice of the
proton as the "characteristic" exchanged species in the Br.,nsted-Lowry
concept was not fortuitous.
Concerning the "ultimate" base , one might choose various smull, highly
charged. ions such as H - , F-, or <Y- , all of which arc indeed quite basic.
However, the electron appears to be the complement ofthe prot on . It might be
objected that the isolated electron has even less justification ns a chemical
entity than the proton, but solutions (and even solids) are known in which
electrons are the anionic species! And interestingly, solutions containing
"free" elect.r ons are very basic. This topic will be discussed in further detail in
the section on liquid ammonia chemistry in the next chapter.
M.asuresof
Acid-Bose Strength
Gas-phase
Basicities:
Proton Affinities
HistDricaOy. acid-base chemistry has been strongly tied to solution chemist ry. not
only in water but in nonaqueous solvents as well (Chapter 10). Chemists knew that
there were strong solvation effects that might be altering or- obscuring inherent
acid-base properties, and they tried various means of estimat inc these effects or
eliminating them through the use of nonpolar solvents . Nevertheless, for many years
the solution thermodynamics of acid-base behavior was only poorfy understood. In
the past 10- IS years a remarkable amount of data on solutionless, that is. gus-pilose.
acid-base chemistry has been collected. Since it is easiest to see inherent acid-base
effects in the absence of competing solvent effects. the following discussion will
proceed: gas-phase -+ nonpolar solvents -+ polar solvents , though this treats the
subject in reverse chronological order.
The most fundamental measure of the inherent basicity of a species is the
affinity. It is defined as the energy released for lhe reaction:
B(g) [or B-(g))
H +(g)
--+
BW(g) [or BH!all
prottlll
(9.47)
Note that the proton affinity (PA) has the opposite sign from lhe enthalpy of reaction
of Eq. 9.47: Proton affinities are always listed as positive numbers despite referring to
exothermic reactions (recall the same convention with electron affinities,
2).
Proton affinities may be obtained in a number of ways. The simplest , and most
fundamental for defining an absolute scale of proton affinities. is to use a Born-Haber
cycle of the sort:
B(g) + H(g)
BH(g)
--l&H....
--r-4/f...
B(g) + H(&)
611 - rA
BH.(g)
(9.48)
Acid-lase Concepts
331
The molecule BH must be sufficiently stable that its bond energy (enthalpy of
atomization, !J.HA.,,) and ioniUttion potential (IE 8 H) can be measured. Once several
proton affinities have been established in this way. many more JlUly be obtained by a
technique known as ion cyclotron resonance spectroscopy and related methods,10
which measure the equilibrium concentrations of the species involved in the
competition:
(9.49}
Gas-phase proton affinities (Table 9..5) confirm many of our intuitive ideas about
the basicities of ions and molecules, though some of the first to be obtained contradicted our prejudices based on solution data (see page 344). The greatest proton
affinity estimated to date is that of the trinegative nitride ion, N 1 -, because of the large
electrostatic attraction of the -3 ion.21 The dinegative imide ion, NH2-, has a very
large but somewhat lower value, followed by amide, NH2, und ammonia. NH3 .
Inductive effects are readily observed with values ranging from nitrogen trifluoride,
NF3
604 kJ mol- 1, through ammonia, NH 3 = 872 kJ mol- 1, to trimethylamine.
= 974 kJ mol- 1 Similar effects can be seen for toluene vs. ben:tene.
acetonitrile vs. hydrogen cyanide, ethers vs. water. and several other comparisons.
Gas-phose Acidities:
Proton loss
Since the proton affinity of a cation indicates its tendency to attract and hold a proton.
its value will also be the enthalpy of dissociation of its conjugate acid in the gas phase.
Consider HF (PAF1.5.54 kJ mol- 1):
tJ.H
+ 1.554 kJ mor- 1
(9.50}
The more endothermic Eq. 9.50 is. the weaker the acid will be. Therefore Table 9.5
may readily be used to compare gas-phase acid strengths, and HF is a weaker acid in
the gas phase than are the other HX acids. as it is also in aqueous solution. In the same
way. acetic acid (PAcH.coo = + 1459 kJ mol- 1) is a weaker acid than trifluoroacetic
acid(PAcF,COO' = + l3.51 kJ mol- 1). Which is the stronger acid. methaneortolue.ne?
Does Table 9.S conlinn or contradict your memory from organic c.hemistry?
Gas-phose Acidities:
Electron Affinities
of the conjugate
The B!linsted gas-phase acidity will be related to the proton
base. However. this gives us no estimate of the relative acidity of nonprotonic (Lewis)
acids. If the electron is the basic analogue of the acidic proon. then electron affinities
should provide inherent g-.Js-phase measure of acidity that parallels proton affinities
for bases.n That they have not been more frequently used in this connection is
lO Aue. D. H.: Bowers. M. T .. In Gus Piton ion Cl..mistry: Bowco. M . T .. Ed.;
Yon. 1979; Vol. 2, Chapler9; Lias. S. G.; Liebman. J . F. ; Levin. R. D. J . Pl1ys. Ch<m.
New
Dntu
t984. IJ. 69S-80ll.

ll
II should be noled Jhat lhc proton aftlniUes of aD of the trinegol.ive and dincpJive anions are
calculalecl by means ofa Born- Haber cycle. Tbey are no1 experimentaDy ac<:<:s.ible since Jhese ions
have no existence ou1side of a sJabilizinK CO'yslal environmcnl-thcy would exolhermic:alty expel an
elcc.lron (see O>apler 2).
21 Tbcre is a compticaling fuc:tcr here in 1ha1 aciclily can refer to I he acceptance of a single eleclron or
an electron pair. Thus a free ndicat miaht bave u hiah electron alllnily bul not have an cmpty,lowJying ubital 10 accq>l an eleCtron pair. TJ-..s. comparison of SO, (EA - lEO kJ mol- 1) as a Slrongcr
acid 1hanSO,(EA 107kJ mol- 111s valid. bul a similar comparison wilh the fn:e raclic:al OH (EA
176 kJ mor'),
nol have a completely empty low-lying olt>itat. is no1.
332
9 Aci.l-lo.. Chemistry
Table9.5
Gos-phooe proton offlllities (kJ mol- 1)

Triaegatmt ions
DnlegotM ions
Uninegotiw Ions
H2 = 424
CH) 174S
C6 H,CHi' 1593
c,H; = 1677
CH4 = SS2
C6 H,CH3 = 794
CN- 1469
(CHJhN- 1658
c;H,rm- -
167t
CH3 NH- 1687
N3 -
"" 3084<'
NH2 -
2S6S4
Neutral molecules
H- 167S
NHi' 1689
NO- ISI9
Nj" 1439
PH; 1552
C 6 H6
C6 H,O- 14SI
t-C4 H,o- - 1567
IS71
IS79
IS92
c;H,o- CH3o-
2318"
OH- 1635
aoo-- 1s73
o; - 1476
CH3C(0)0- 14S9
HC(O)O- 1444
S94
974
954<
953<
935<"
919<
= 899<
NH1 = 872
CH3CN = 789<
HCN = 796
NF3 = .604
NO ... 531
N 2 = C94.S
(CH,);,P=
(CH;,)zPH =
CH3 PH2 =
PH3 =
Pf1
AsH; ISIS
= 759
CO=
(CH,);,N =
(CH;,)zNH =
C,H, N =
;H,NH2 ""
CH3NH2 =
""
950
90S
8S4
789
697
(CH,>1As "" 893
AsH1 = 750
Clf3C(O)NH2 = 863
C6 H,OH = 821
t-C4 H,OH = 810
i-C3 H7 0H = 800
C:tH,OH = 788
CH10H = 761
(CH,)zO "" 804
(CH,).zCO = 823
H 2CO"" 718
CH3N02 "' 750
H20 = 697
HOOH "' 678
H02 - 661
CH1 C(O)OH = 796
HC(O)OH 748
probably because or the filet that rormerly there were rew electron affinity values
known ror molecules (Table 2.6). Those Lewis acids having large electron affinities are
apt to be strong acids. This idea is especially powerful when applied to metal cations.
Recall that the electron affinity or a monopositive cation is the same as the ionization
energy or the metal atom. From this pain( or view it is readily apparent why the alkali
and alkaline earth mdals are such weak Lewis acids when compared to the transition
metals:
Measures of Acid-lou Str..,gth
333
Table 9.5 (ContinveJ)
Gas-t>foo.. proton offrities (kJ ...or1)

Trinegatift ions
Oinegotift ions'
Neutral molec....
Uninegative ions
a<r -
NO}=
NO)
CFJC(O)O-
FSO) ""
CFySO) ..
1.502
1421
13S8
13SI
1285
128&'
CF,C(O)OH "' 707
(CHJhSO "' 884
co. -
548
o;- 422
CHls- 1493
1469
sw -
SeH- 1466
r ISS4
a - - J39S
Br- 1354
1- - 131S
= 839
CHJSH 784
H..S = 712
H;zSc:
= 717
HF"' 489.S
HCI"' S64
HBr 518
HI= 628
He:- 178
Ne = 210
Ar= 371
425
Xe
496
IllS< Mn(CO)j < 1340<'

1380 < Rc:(CO)j < 1395Co(PF,>; < 128&'
.. 778
Unless olherwise noced, aD data for neulnll moleCUles are from Lias, S. G.; Liebman, 1. f .:
Levin. R. D. J. Pity$. O.tm. R(/. Doro 1984, /J. 69S-808, and for anions are from Lias, S. G.:
Bartmess. 1. E. : Uebman, 1. F.; Holmes, 1. L.; Levin, R. D.: Malard, W. G. J . Phys. Chnn.
Rtf. DDIII 1981, 11, 1-861.
Dineplive and trineptlvc ions have no cxistenc:c oulsidc or a system. such as a lallice, thai
stabilizes lhem. 1Rese values are r.uhet crude cs1lmatca from Bom- Hobcr cycles and indicate
the n:lalive dilliallly or pullina a proton away from their COfliuante acids.
MeoiNcr, M.; Sieck, L.
w. J. Jim. Clwm. Soc. 1991, II J, 4448-4460.
4 Waddinaton, T. C. Jldv. lnorr. Chtm. Rodlochtm. 1!159, I,
157-221.
Miller, A. E. S.; Kawamura, A. R.; MiDc:r, T. M. J . Jim. Chtm. Soc. 1990, Ill, 4S7-4S8.
Vigjno, A. A.; Hcnclunan, M. 1.; Dale. F.; Deal<yM, C.; Paulson, J. F. J. Jim. Chtm. Soc.
1992. 114, 4299-4306. HCo<PF,)4 is lhc: stronacs ps-plwe acid rq>oncd 10 dale, donalilll
protons to Ill anions listed above il.
K+
+c:------> K
Ca2+ + e- -----> ca
Mol+ +e----+ Mn+
EA
(9.51)
EA
=- 114S kJ m ot -
(9.52)
EA
(!).53)
419 kJ mol -
= t S09 kJ mol -
Pt2 + + e- ---+ Pt+
EA- 1791 kJ mot -
Co 3 + + e- ---+ Co2
EA - 3232 kJ mor
(9.54)
,,.55)
334
9Acid-lase Chemisary
This gets us back to the fundamental property of the ionization energy of a metal that
determines not only its redox chemistry but also its tendency to bond to anions and
other Lewis bases.n
lewis lnteraction.s
in Nonpolar
Solvents
The evaluation and correlation of strengths of Lewis acids and bases have attracted
the interest of many inorganic chemists. Recently gas-phase data have become available, but before that many systems were studied in aprotic, nonpolar solvents. Even
today, such solvents allow the collection of large amounts of data by various methods.
Solvation effects will be small and, it is hoped, approximately equal for reactants and
products such that their neglect will not cause serious errors.
It is common to equate the strength of interaction of an acid and a base with the
enthalpy of reaction. In some cases this enthalpy may be measured by direct calorimetry: fJ.H
q for an adiabatic process at constant pressure.
Often the enthalpy of reaction is obtained by measuring the equilibrium constant
of an acid-base reaction over a range of temperatures. If In K is plotted versus liT. the
slope will be equal to -llH/R. Thus various experimental methods have been devised
to measure the equilibrium constant by spectrophotometric methods. Any absorption
which differs between one of the reactants (either acid or base) and the acid-base
adduct is a potential source of information on the magnitude of the equilibrium
constant since it gives the concentration of two of the three species involved in the
equilibrium directly and the third indirectly from a knowledge of the stoichiometry of
the reaction. For example, consider the extensively studied reaction between organic
carbonyl compounds and iodine. The infrared carbonyl absorption is shifted in fre;.
quency in the adduct with respect to the free carbonyl compound. Thus the equi
librium mixture exhibits two absorption bands in the carbonyl region of the spectrum
(fig. 9.1) and the relative concentrations of the free carbonyl and the adduct can be
obtained. 24 Alternatively, one can observe the absorption of the iodine molecule, 12 , in
0.0
g0.2
...
j
< 0.4
0.6
t.O
t690 t680
t670
t660 t6SO
t640 t6)0
t620 t6t0 t600
fRqucncy (cm" 1)
fig. 9.1 Jnfr.>rcd absorption spectra of dimethylacctamide-iodine system: (II dimethylacetamicl.: only: C2-6) increasing concentrations of iodine. Peak at 1662 em" ' is from free di
methylacetamide, t hat at 1619 em- ill from the
adduct. !From Schmulbach. C. D. ;
Drago, R. S. J. Am. Cloem. SrJc. 1960, 82. 4484. Reproduced with permission.)
n For a
useful discussion of the chemical (lropertics of metals, as rel:ued to their ioni:uuion
energies, ""e Ahrens, L. H. Ionization Pountiuls; Pergamon: OJ<ford, 1983.
14 Schmulbaeh.
C. D.; Draao. R. S. J . Am. Cbrm. Sar. 1960, 82. 44(14...4431.
MeaS8res of Acid-Bose Slrenglh
335
the 300-600 nm portion of the visible spectrum. Again. the adduct absorbs at a
different frequency than the free iodine and the two absorption maxima provide
information on the relative concentrations of the
present.2l
Two complications can prevent a simple dete rmination of the concentration of
each species from a measurement of a bsorbance at a chosen frequency. Although
most of the acid-base reactions of interest result in a
stoichiometry. one
cannot assume this a priori, and
and three-to-one adducts might also be
present. Fortunately, this is usually an easy point to resolve. The presence of an
isosbestic point or point of constant absorbance (see Fig. 9. 1) is usually a reliable
criterion that only two absorbing species (the free acid or base and a single adduct) are
present .26
The second problem i.s somewhat more troublesome. The separation between the
absorption maximum of the adduct and that of the free acid (or base) is seldom large
and so there i.s considerable overlapping of bands (see Fig. 9. 1). If the absorptivities of
each of the species at each frequency were known, it would be a simple mauer to
ascribe a proportion of the total absorbance at a given frequency to each species. It is
usually a relatively simple matter to measure the absorptivity. , of the free acid (or
base) over the entire working
Since it is often impossible to prepare the pure
adduct (in the absence of equilibrium concentrations of free acid and base). its
absorptivity cannot be measured. Howe ver. if the equilibrium is studied at two
different concentrations of acid (or base). it is possible to set up two simultaneous
equations in terms of the two unknowns K and and solve for both.21
Alternative methods of measuring the enthalpy of acid-base reactions involve
measuring some physical prope.rty which depends upon the stre,.;th of the interaction.
In general . such methods must be calibrated against one of the previous types of
measurement. b ut once this is done they may often be extended to reuctions that
prove difficult to measure by othe.r means . One example is the study of phenol as a
Lewis acid.:!II Phenol forms strong hydrogen bonds to Lewis bases. especially those
that have a donor atom with a large negative charge. The formation of the hydrogen
bond alters the electron density in the 0-H group of the phenol and the 0-H
stretching frequency in the infrared. Once the frequencies of a series of known
phe nol-base adducts have been used for calibration (Fig. 9.2). it is possible to estimate
the enthalpy of adduct formation of bases with similar functional groups directly from
IR spectra.
A second method involves the relation between s char.1cter and NMR coupling
constants. Drago and
have shown that there is a good correlation be
tween the IIIISn-H coupling constant in chlorotrimethylstannane-base adducts and
the stre ngth of the base-tin bond. In the free stannane the strongly bonding methyl
groups can maximize their bond strength. s character. and thus
It has been
suggested that the stronger bases force the tin to rehybridize to a greater extent (-sp3
"DraGo. R. S.: 0111son. R. L.: Rose. N.J. ; wenz. D. A. J. Am. Clrm. St>c. t'X>t . 81. )ST.!-3575.
""n.e prc<ent d iscussion ol i.wsbcstic poiru is ovcnimpliliecl: the rC<>dc:r is w:1rned that ooe con gel
into clifficutlic.< with such

For runhc:r di.cu..<ion olthc usc or
points.
see Cohen, M. D.; Fischer. E . J. Chtm. Soc. t'X>2. 3044-JOS2;
R. G .; Drago. R. S. 1-11
CNm. t976, /J, 2Qt0-20tt; Styncs. D. V. lnorR. Clrtm . t975, 14. 4SJ-4S4.
n Rose, N. J .; Drago. R. S . J . Am. CNm. Soc. t959, 6/,
:za Epley. T. D.: Dr.,o. R. S . J. Am. Orrm. Soc. t'X>7.89, sno-snl: t'X>9. 91. 2883-2l!90. One must
be carerut in the choice ol bases. Sec Vosel. G. C.; Draco. R. S. Ibid. t970. 92, SJ47-SJS t.
29 BoUu, T. F.: Drago. R. S. J. Am. CNm. Soc. 1966,88. S7l0-S734.
336
9Aeicl-8ase Che111istry
40
)()
10
0
100
200
)()()
400
500
600
Allo-H (tm.')
Fig. 9.2 RdaJian bclween the erullalpy of rormation or base--phenol adducts and t he
stretching frequencies or the 0- H bond in the phenol. Bases: (a) acetonitrile. (b) ethyl
acetate. (c) acetone, (d) telrahydroruran. (e) di1!1"'thylacetemide. (0 pyridine, (g) triethylamine. (from Epky. T. D. ; Dn,o. R. S . J. Am. Cl.,m. Soc. 1961 . 89.
Reproduced
with permission.}
in free Me3SnQ; -sp3d in the limit of stroog base adducts) than weaker ones, and thus
the change in s character of the Sn - C bonds.
Systematics of
Lewis Acid-Base
lnferad ions
Drago and cowott.ers have proposed a number of ways of expnssing enthalpies of

reactions in terms of contributing parameters of acids and bases. The first was
(9.56)
where l1H is the enthalpy of formation of a Lewis acid-base adduct, ,. and C,. are
parameters characteristic of the acid. and 8 and C8 are parameters characteristic of
the base.JO The E parameters are interpreted as the susceptibility of the species
to undergo electrostatic ("'ionic" or dipole-dipole) interactions and the C parameters
are the susceptibility to form covalent bonds. From this we expect those acids which
bond well e.lectrostatically (,.is large) to form the most stable adducts with bases that
bond weD electrostatically (since the product ,.8 will then be large). Conversely.
acids that bond well covalently will tend to form their most stable adducts with bases
that bond well covale.ntly. Some typical values of,., 0 ,
and C8 arc listed in
Table 9.6. The application of Eq . 9.S6 may be illustrated with the reaction between
pyridine( = 1.78. C .. 3.S4)and iodine( 0.50. C 2.00: by definition. the origin
of the scale; see Footnotes 30. 36).
c,..
,. ,.Eb
C,.Ca (O.SO
= (7 .97 kcal mol-l1H.a.p
= (7.8
1
) a
1.78) + (2.00
3.S4)
33.3 kJ mor '
(9.57)31
kcal mor ' l - 32.6 kJ mol- l
The importance of the E-C parameters is manifold. First. they enable predictions
to be made of the enthalpies of reactions that have not been studied. Thus the
parameters in Table 9.6 and comparable values were obtained from a few hundred
"'OnJco. R. S.: Wayland. B. B. J. Am. Clirttt. Sue-. 19'5. 87. 3S71-3.117. Cnao. R. S.;
G . C.;
Nudham. T. E. J. Am. Ch,m. Sue. t971 . 9J. 60t4-W28.
11 The original -C sale and all subsequent modil\caliom have been in l<c:al mol - o. One c:aJO a!W
1
onultiply 111c reou11 by 4. 114 10 oblain
in I<J mol- crtate a new scale in wt.ich all !he
1
panmeten in Table , ,6 are muljpied by 2.0.1 ti<J mor- lor./(ltcal mol- )1./l.
T....._U
Acid end base
....,......en
E,.
c.
o.so
U4
0.56
2.03
1.77
1.25
0.77
3.69
2.27
1.36
1.49
1.72
2.07
1.34
1.14
0.61
0.54
1.48
0.10
1.32
1.70
2.00
0.13
1.52
0.30
0.50
0.75
1.46
0.74
1.07
0.51
0.46
0.86
1.06
0.69
0.90
0.36
1.22
1.14
0.27
0.91
2.71
Jlasec
Ea
c.
NH3
CH3NH2
2.31 . 2.04
2.16 3.12
1.80 4.21
1.21
5.61
2.35 3.30
1.32 5.73
0.80 6..72
1.78 3.54
1.74 3.93
1.76 3.72
1.78 2.81
1.64 0.71
1.74
1.26
1.63 0.95
1.62 0.98
2.19
1.31
1.80 1.63
1.86 1.29
1.64 2.18
1.70 2.02
0.24 3.92
2.40
1.47
Acid
1.
H20
.......
SOz
HfO
HCN
CH30H
HO"
C6 H5 0H
(CH 3hCOH
HCCI3
CH3COzH"
CF3 CH 2 0H
Asf1
Fe(COfs
CHft
(CH,),N
C5H5 N
4-CH3 C,H4 N
3-CH 3C,H4 N
3..(lC5 H.N
CH1CN
CH1C(0)CH1
CH1C(Oio<;H,
HC(O)N(CH1) 2
(C2 H5)z0
O(CH2CH 1)z0
(CH2 )40
(CHzlP
(CH3)zSO
R,.
0.20
o.ss
0.47
0.54
0.39
O.S6
o.ss
0.39
0.48
0.4S
0.63
0.38
0.41
0.46
0.87
0.84
0.78
1.00
0.27
0.61
T,
O.S6
O.S9
0.64
0.15
0.54
0.76
0.83J
0.73
0.7)J
0.74J
0.83
0.80
0.86
0.89
0.74"
0.76
0.71
0.1S
0.14J
I. IOJ
0.65
Acid
H+
CH+
u,
K +b
No
NH
b
(CH3)1NHi
(CH 3 ) 4 N+6
CsH5NH+" b
(CzHshNH+
(CH,)3NH+b
HO+
)
+
(H 20)2 H
(H 20),H+
(H 20)4 H+6
(CH3J,Sn+
(C5 H5)Ni +
(CH3 )NH;6
C,H,NO
(Of3hP
(CH 5)z0
(CH,lzS
CH30 H
HzS
HCN
H2co
CH3Qh
CH3CHO"
Hz<Y'
(CH 1 ) 3COH"
...
Br-
1-
eN-
OH -b
CH30 - b
E,.
c,.
R,.
4S.OO
19.70
11.72
3.78
O. lb
4.31
3.21
1.96
1.81
2.43
2.60
13.27
11.39
11.21
10.68
7.05
11.88
2.18
13.03
12.61
1.4S
0.11>"
6.86
4.31
0.70
2.36
130.21
r.
Ca
2.29
1.46
1.68
0.25
1.80
1.85
0.70
0.04
1. 19
1.56
2.54
1.76
2.28
1.92
1.75
9.73
7.50
6.74
S.48
7.23
10.43
10.03
2.33
3.44
I .SO
3.75
0.65
1.09
0.45
I.S6
0.10
0. 10
0.10
0.81
0.10
1.22
0.62
4.28
3.76
3.21
2.97
6.52
4.60
4.42
1.33
2.0S
1.33
7.89
6.03
4.66
4. 11
3. 1S
3.49
2.38
55.09
24.21
20.79
45.99
18.52
2o.n
8.33
21.72
11.81
IS.95
20.01
7.36
2.34
3.25
26.93
32.64
20.68
Ta
0.67
0.90
0.73
1.07
0.70
0.70
0.81
1.13
0.90
0.76
0.23
0.74
0.43
0.71
o.ss
37.40
12.30
5.86
6.26
9.20
50.73
33.77
Drago. R. S.; Ferris, D. C.; W0111. N.J. Am. CNm. Soc:. 1990, 112, 89Sl-8961. Ongo, R. S.;
Wong, N.; Ferris, D. C. /bid. 1991, 1/J, 1970-1977. Reproduced with pcmiuicn.
Tcn1a.1ive perarnraers from imilcd cnthalpy datA.
If not indicaled otherwise, 1ht basu in 1h;, !able have 8 and Ca cktcrmincd from Jhe li1 of
neutral acid-neutrol base adduc:ts (Footnole 30).
TM E. and Ce for 1llese ba= are wed ddetmincd. TM T8 value$ ate I<!UIIve foe IIley ha""
been de!ermirrd rrom limited dati. See the oricinal
rw methods llld accuracy or lht
value1
I
I
337
338
9 Acid-lase Chemistry
reactions of acids and bases, but they can be used to predict the enthalpies of
thousands of reactions. For example. uccurate values can be obtained for reactions
such as:
(CH 1hN + S02
t.H.,k:
= 38.5
--+
(CH:J3 NS02
(9.58)
kJ mol- 1 (9.2 kcal mor 11
llH0 "" = 40.2 kJ mof" 1 (9.6 kcal mol- 11
llHcok = 23.4 kJ mol- ' (5.6 kcal mof" 1)

t.HP = 23.4 kJ mor t (5.6 kcal mor 1)
The second item of importance with respect to parameters of this sort is that they
enable us to obtain some insigJ!t into the nature of the bonding in various systems.
Thus, if we compare theCA and A parameters of iodine and phenol, we find that 12 is
twicen as good a "covalent-bonder" as phenol, but that the latter is about five times
as e.ffective through electrostatic attractions. This is not unexpected inasmuch as
phenol, C6 H 50H, is a very strong hydrogen bonding species. In contrast, iodine has
no dipole moment but must react with a Lewis base by expanding its octet and
accepting electrons to form a covalent bond.
A similar effect can be observed in the bases. The 8 value of dimethylsulfoxide,
(CH3>zSO. is much larger than Jhat of diethylsulfide,
corresponding to the
large dipole moment of(CHV!SO (p. = 13.2 x 10-.10 C m; 3.96 D) compared with that
30
of the latter (JL = S.l4 x 10- C m; I.S4 0). On the other hand, the C 8 values are
reversed, corresponding to the enhanced ability of the sulfur atom to bond covalently
to the acid.
Drago and coworkers have modified Eq. 9.S6 by adding a constant specified by
the acid (acceptor): n
(9.60)
Eq. 9.56 deals with a simplified situation: the approach of A and 8 to the bond
distance with a resultant EA8 electrostatic energy based on the inherent electrostatic
bonding capabilities (dipole-dipole interactions. etc.) and a resullant C AC8 term based
on the inherent covalent bonding capabilities (related to overlap, etc.). This approximation is quite good for neutral species. and small discrepancies (such as the increase
in covalency through electrostatic polarization) could be (and have been) accommodated by incorporating them into the and C parameters.J4
One muSI be careful in m:1king comparisons using these oombers. A comp:uison of Eo, 10 E.,0 H is
v:llid, but one c:oonot compare the E ond C pa1"811ld= dirccJiy apinSI eoch other for a sinaJe
species becouse of the necessory, arbiorary assii!Jlments: Eo, O.SO; C11 - 2.00.
>. Drago. R. S .; Wong. N .; 8Ugricn, C.: Vogel, G. C. /not'fl.
1937.26.9-14. 'Ole ccn.stant Wis
for an energy olways ASSOCialed wi1h a ponicular rtaclant, such as the enthalpy of dissocia1icn of a
dimer ollowins il to react as a mcnomer.
>2
.. By adjusling E and C lo sive the best fil of the experimental dala. somr of the nestect of transfer
energy can be alleviated.
Measures of Acid-llase Strength
339
If the amount of charge transfer from base to acid is large, however, as it must be
if either species, or bot/e. is an ion. this energy must be explicitly accounted for.
Fundamentally. it is the energy change as an atom (ion) runs along the energy-<:harge
curve of Fig. 5.32. Thus. this transfer energy term parallels ioniUition energies and.to
a lesser extent. also involves electron affinities.Js It can be treated by adding a term
composed of two additional parameters: R,. (receptance. acid) and T8 (transmittance.
base):l<>
-llH = ,.8
+ C,.C8 + R.,1;,
(9.61)
Two proce.sses iDustrate the application of Eq. 9.61:

H!O +
Ir -
H30+
-MI.r.r> = 695 kJ mol- 1 (166 kcal mor'>
- t.Hc.k .. ,. 8 (102.6} + C,.Ca (1.3} + R,.T8 (56.0} =

669 kJ mor- (159.9 kcal mol -
+ H+
- llH ,.
-Mi.-
(9.62)
(9.631
1)
= 803 kJ mol- 1 (192 kcal mol- 1)
(9.64}
= ,.8 (7.5.6) + C,.C8 (19.5)
+ R,.T8 (95.0} =
(9.65)
79.5 kJ mol - 1 (190.1 kcal mol- 11
The last term represents the energy accompanying the transfer of electron density
from an electron-rich base to an electron-poor acid. The details need nol concern us.
but the results certainly are of interest:
I. To obtain a complete picture of bonding in acid-base interactions. three
separate factors must be taken into account: althe electrostatic energy of the
acid-base interaction; b) the covalent energy of the acid-base interaction: c)
the energy involved when electron transfer takes place. These results were
anticipated in principle on the basis of Mulliken-Jalfe electronegativity.n
2. In the gas phase the proton is a tremendous acceptor of electron density. and
the
energy is very brge. This transfer energy has already been largely
"spent" for the solvated proton (e.g .. hydronium ion) in solution where the
reactions are of a displacement type:
HJO+
---+
H10 + NH,t
(9.66)
" The: nqlcxt o( the clc:ctron 31linity in clectronq:ativity

oflcn be justified bec:>usc in XM
let E. + EA.) the v:llue of IE. may be an order of magnitude lartct" !hun that of EA.. Thus
por:uneter sysiCm IIIIIY be upf"oxinwwJ
one-f>:lr:unctcr equal ion. However. the recent devel-
opments in acid-base theory repot'led from here to the end of tile chapter rcftcct the re:lliulion that
acid-buc inler.M:,Iions arc more subcle than oneparurnctcr cqwuitlns predict. For o. direct complll'i$oo, note how wei a one-ponrnetcr clectroneamivily sy.ecm IP:oulingl works, in general. even
Jhovah eleclt'One'lllvily is obviously a two-parometcr function
Sec also di.cussion on Past )4t.
,. Dnso. R. S.: Ferris. D. C.: Wong, N. J. Am.

1990, 112. 89$)-8%1. Oroao. R. S.;
Wong, N.; Fcrrit., D. C. Ibid. !991, IIJ. 1910-tm.
7
J Evans. R . S.; Huheey, J. E. J. lnr1rg. Nud. Chcm. 1970, J2. m-793 . The
here invOlved
lhe reverse process: First dectronqnJivily equaliution Wi1S assumed !equals Optimizing the dec
tron tnmsl'er energy I and then modific:.tims Cor
covalent contributions were added. This
worked best on ior>-ion incenctions 1u + f"' u f"')
poorly on neulral moleculd (Huheey and Evans. unpublished). See page lSI.
340
9 Acid-lase Clte.,istry
3. The nearest anionic analogue of H + is the F- ion. Some of the calculations for
it are at first surprising, but parnllel those of the proton and are acceptable
under closer scrutiny: (a} F- forms a stronger CCVtiiCnl bond than a- (> Br- >
1-);.NS (b) F- is a very strong base with a largt transfer of electron density to
the acid. This is a result of the low charge capacity (low electron affinity} of
fluorine.
4. As with any successful model. exceptions call attention to themselves and
signal the existence of unusual effects: repulsions, 1T bonding, or adduct geometry variation.
Bond Energies
There are two ways to approach the formation of a polar bond X6+ - y&-. We have
already encountered both. One is to consider the formation of a nonpolar molecule,
X- Y, followed by an electronegativity-controlled shifi of electron density from X
towards Y. Alternatively, one can form the ions x and y-, followed by their
interaction. We can view the Iauer as the Flijans polarillltion of y- by x, or basic
attack of :Y- upoo x. Whatever model is used, there occur. in one form or another,
three contributing energies:
I. The covalent tnugy, E,. arising from electron sharing. It is a maximum in a
homopolar bond and decreases with ionicity.
2. The Madtlung tMrgy, E,... arising from the coulombic attraction of the partial
charges:
EM
6oe2
(9.67)
41rrfo
This energy is termed the Madelung energy since it represents a " lattice
energy" internal to the molecule with a Madelung constant. of course, equal to
1.00. It is a maximum in a purely ionic bond (6+ ,. .z+) and decreases to
whatever extent the charges on X and Y dec.rease.
3. The tltctrotrtgativiry tnugy, E or IE-EA tnugy arising from ionillltion
affinity terms in the total enerey sum. It is a more complex
function thanE,.. and Er but it will be clarified by some examples below.l9
Consider Pauling's Ionic resonan,t

of a principally covalent bond with a
little ionic character from the difference in electronegativity. To a first approximation,
the ionic resonance energy may be equated with the sum of the Made lung ene.r gy. Ew
and the electrone.gativity energy. ,.. which stabili:z:es the XY molecule more than the
small loss oC covalent energy destabilizes it . The simplest example oC these three terms
has already been encountered in the form of the Born-Haber cycle and the
Bom-Landt Equation (taken only to the point of isolated gas-phase molecules with a
Madelung constant of 1.00). The equaaion in that form shows that the gas-phase ion
pairs (ionic molecules) are stabiliud by the Madelung energy holding them together
and are destabilized by the ionization
affinity energy that had to be
paklto form the ions. Note that if we brought two ions together (acid-base reaction)
ll This is rnenJy lfle
o( smaUa""villa bclter
1M usual prejudice thai
cannot bond covalcMlY arises from the urlortullllc tendency to overc"'fflwiu Ihe diffu
n>a$ b e - covalan and ioric bondi,._ Bondlrc is too often ch:ar:oc:tcrized as covalnt 01' ionic,
rather than possi>ly a>valcnt MJ ionlc.
,. See also Evans, R. S.; Hubecy, J. E. Clwm. Pltp. Lm.
am. 19. 114-116.
Meaaures of Acid-Base Strength
341
and they were not compleuly ionic (no compounds are), electron density would liow
from the anion (base) to the cation (ucid); there would be some Joss of Madelung
energy (the charges decrease) but a stabilization of the formerly unfavorable EaE-EA
as the metal flows down the energetically steep part of curve Fig. S.34a (A+) and
the nonmetal flows up (in the case ofF-. initially down) the relatively mild slope of
Fig. S.34b (B- ). To say it another way Fig. 5.35 will be approximated. no matter
whether we approach equilibrium from A + BorA+ + :B-. Finally. inherent in the
bond A- 8 is the covalent energy term arising from the overlap of orbitals, whether it
be from the covalent bond picture or polarization of ionic species.
We can oow examine in fUrther detail the ,C. R. and T parameters of Drago's
system. We have seen that A8 and CAC8 terms indicate tendencies to form
electrostaiic (M) or covalent (r) acid- base interactions. Finally, the RATs term
provides a measure of Ex which can be clearly shown to be related to an IE-EA energy
(see pa!le 339). Note. however. that in contrast to the ion-pair example given above,
where 1&-EA (Ex) was destabilizing, in covalent acid-base reactions of ionic species,
term will be strongly stabilizing. This is especially true of species such as l r
and F- . in accordance with the electronegativity argument given above . and the RATs
term will be a major contributor to the stabilization of the donor-acceptor bond.
An example of the importance of the ene.rgy associated with this transfer of
electron density is discussed by Drago. Because of the very large value of e.lectron
transference energy (resulting from the high ionization energy of hydrogen}. the
energy associated with the gas-phase attachment of H + to bases (proton affinity) is
unique; other acids, including the aqueous hydronium ion. are different. This is
because the bare proton has an extremely high charge/size ratio and releases an
extremely large amount of Ex upon adduct formation (RH ; 130.21)compared to aU
other acids that have several atoms over which to delocalize the cationic charge. This
is analogous to the b parameter of
electronegativity (see Chapter S),
which measures the capacity of a group to " soak up" charge and stabilize it. Thus
methyl groups can stabilize charge on a cation (have a low electronegativity b term}
for exactly the same reason that as ions they have lower R A values than the proton
(RMc' - 5S.09) .
Steric EHects
In reactions betwee.n Lewis acids and bases such as amines and boranes or boron
halitles. bulky substituents on one or both species can affect the stability of the
acid- base adduct. Perhaps the most straightforward type of effect is simple steric
hindrance between substituents on the nitrogen atom and similar large substituents on
the boron atom . Figure 9.3 is a diagrammatic sketch of the adduct between molecules
of tripropylamine and triethylborane. This phe.nome.non is known as front or "F-
fig. 9.3 Tripropytuninctriethylborane adduCI

illustrating stem hindrance
between the bulky substiluenl$ on the nilrogcn
and the boron.
342
9 Acid-Boa Chemistry
strain"" and can have a considerable influence on the stability of the adduct since the
alkyl groups tend to sweep out large volumes as they rotate randomly.
A second. similar effect is known as back or ""BStrain."" It results from the
structural necessity for the nitrogen atom in amines 10 be approximately tetrahedral
(spl) in order to bond effectively through its lone pair. If the alkyl groups on the
nitrogen atom are sufficiently bulky. presumably they can force the bond angles of the
amine to open up. causing more s character to be used in these bonds and more p
character to be left in the lone pair. The extreme result of this would be the formation
of a planar. trigonal molecule with a lone pair in a pure p orbital. poorly suited for
donation to an acid (Figure 9.4).
Related to B-strain. but less well understood. is .. !-strain.. (for internal strain). In
cyclic amines and ethers, such as (CH 2),.0. the basicity varies with ring size. In such
compounds the hybridization (and hence the overlapping ubility and electronegntivity)
of not only the basic center (N. 0. etc.), but also of the carbon atoms in the ring will
vary with ring size. and there are no simple rules for predicting the results.
When the basic center is exocyclic. as in lactams.lactones. etc . the results can be
interpreted in a straightforward way analogous to the argument given previously
(Chapter .5) for biphenylene. Consider the series of lactams:
6 6 u
0
CH
3....._
>
CH
J'-N
CH
>
As the ring size is reduced. the internal bond

must reduce. and the hybridizntion of the cyclic atoms must have less s character and lower electronegntivity.
Toward the exocyclic oxygen atom. the basic center.4o the cyclic carbon atom must in
tum exhibit greater s character and a high electronegativity. The carbonyl groups in
small ring compounds are therefore less basic.4 '
"Proton Sponges"
Although steric effects and strain always work against basicity in simple molecules
and monocyclic compounds. there are a few compounds in which the steric and str.Un
effects stabilize the H adduct. increasing the basicity. An example is the 1.1!bis(dimethylamino)naphthalene molecule in which steric hindrance of the methyl
groups and repulsions of lone pairs on the nitrogen destabilize the l"rec base:
(D)
Cbl
1<1
Fig. 9.4 B-strnin in substiluted amines: tal small substituents. no str:>in. good base;
(b) moderate strain from intermediate-sized substituents. some rchybridization; (c) extreme
bulkiness or substituents. nitrogen atom forced inao planar. sp> + p hybridization. weak
base .
.. Sec Problem 9.16.

41
Fitgueiras. C. A. L.; Huheey. J . E.
Org.
11176. 41. 49-SJ.
Measure af Acid-Base Strength
343
(9.68)
Such compounds are very basic CpKb = 1.9; cf. NH 1 , pK"

4.74; 1-dimethylnminonapthalene , pK" = 4.57). and have been nicknamed "proton sponses" from
their avidity for hydrogen ions.42 The strong, symmetric N---H ---N hydrogen bond
(see Chapter 8) stabilizes the
acid. Note, however, that a stcond proton
cnnnot be added without incurri._ the original steric problem: Diprotonation is only
half complete in 86% sulfuric acid!
Solvation EHects
and Acid-Base
"Anomalies"43
Paradoxically. data on acid-base behavior in aqueous solution have been collected

over a longe.r period than for any other system. yet until recently have been understood less. This is partially due to the fact that theories had been constructed to
account for the aqueous data without knowledGe of acid-base behavior in the absence
or near absence of solvation effects. For example, F-strain and B-strain have been
invoked to account for the anomaly of the pK" of trimethylamine when compared to
the less substituted amines and ammonia (page 329). We now know that when the
basicities of methylamines are measured in the gas phase. they increase regularly NH 1
<
< (CH:JhNH < (CH1 J1 N (see Table 9.S). Therefore the "anomaly"' of the
hydrobasicity of trimethylamines must lie in some solution effect. Solvation
gen bonding will tend to increase the apparent strength of all amines because the
positively charged ammonium ions will be more extensively solvated (6H ten to one
hundred times larger) than the uncharged amine.
R
R N + 2H.O
/H
OH + R-W - H O
I
'H
(9.69)
'/
H
RNH + 4H.O
l
I
I
OH- + R-W - H O
/H
' H
(9.70)
1;1
/o,
.u For a review of 51eric: eiTcciS and lxl.<icity, i"ctuclinll cyclic compounc!s and
protOn sponacs. sec

Alder. R. W. Clwn. Rrv. l!'ll9. 89. t2tS-tm . Note th:atlllllny Pf'O(on spoqtS lave low solUbilities
in ll"rt water.
41 Arnett. E. M. J. Clwm. Elluc. 1915.62. 385-391. For a loo1ccr cliscussion than liven here and moce
T. H.; Ridlanlson. K. S. ltlcM11ism fJitd Tlwory ill Org41tic Clwntbtry.lrd
ed.; Harpec- cl Row: New Yort. t987; I'P 296-Jt6.
344
9 Acid-Base Chemistry
Hence the b11sicity of the a mines is enhanced in proportion to the extent of solvati'on of
the conjugate ammonium ion. and the energies of solvation are RNH; >
>
R 3NH+ . This is the reverse order of increase in basicity that results from electronic
(inductive) effects. Two opposing, nonlinear trends will give a maximum or a mini
mum. Therefore it is not surprising to find a maximum in basicity (as measured in
aqueous solutions) for the dialkylamines. When these reactions are analyzed by a
Born-Haber-type cycle (see Problem 9.28) the effect of solvation can readily be seen.
When each hydrogen bonding positive atom on an ammonium ion is replaced by a nonhydrogen bonding alkyl group. the ion loses about 30 kJ mot- of hydration energy. 4 l
Many of the "anomalies.. are historical artifacts: Accurate experimental data
for species in solution had been accumulated for decades, and corresponding theories
had been proposed long before the first gas-phase data were collected. For example. it has been found that the acidity of water and alcohols goes in the order H2 0 >
R(I"))H > R(T)OH > R(3)0H with the .. explanation.. being that the electronreleasing alkyl groups force electron density onto the oxygen of the conjugate base
making it more basic. But note that the electronegativities of branched and unbranched alkyl groups are practically identical. and if there is any trend. those groups
having more carbon atoms are slightly more electronegative: Me = 2.30. Et = 2.32.
i-Pr = 2.34, /-Bu = 2.36 (see Table S.7). However. these groups differ significantly in
their charge capacity (Chapter .S). Thus highly branched groups are both beuer dorwrs
(when attached to electronegative centers) and better acceptors (when attached to
electropositive ce.nters). Seerringly paradoxically (but refer again to Figs. 2.13 and
5.34) o- is electropositive: The oxygen atom will be stabili1.ed if the anionic charge is
delocaliud. This can best be accomplished by groups with larger charge capacities.
Relative to the hydrogen atom (1 .0). the charge capacities of groups are Me = 2.8.
Et 3.4. iPr = 3.9, and tBu = 4.2. The net result is that in gas-phase reactions with
no complicating solvation energies, the order of basicity is OH - > R(t)o- >
R(ZO)O- > R(J")O- .44
So why the reversal of basicity as one proceeds from the gas phase to solution?
Once again, solvation effects overcome inherent electronic effects. As in the case of
amines. hydrogen bonding is the predominant factor. and as the organic portion of the
ion grows, it becomes increasingly like a ball of wax. The anion loses the special
solvation stability normally enjoyed over neutral molecules and thus more readily
accepts a proton. The enhanced basicity of the tbutoxide ion arises not because the
electron density on the oxyge.n is higher (it is lower).' but because the anion lacks
stabilizing solvation.
Hard and Soft

Adds and Bases
For some time coordination chemists were aware of certain trends in the stability of
metal complexes. One of the earliest correlations was the Irving- Williams series of
stability.46 For a given ligand, the stability of complexes with dipositive metal ions
<
< Mif < MnZ+ < Fe2 + < Co2 < Nil+ <
follows the order: Ba2+ <
Cu2 > Zn2 +. This order arises in part from a decrease in size across the series and in
.. Btauman, J . 1.; Bl:lir, L. K. J. Am. Chm. Soc. 1968.90. 6561-6562; 1970, 92, S986-S992.
4'
Baird. N. C. CDII. J . Chm. 1!'69. 47, 2306-2307; Lewis. T. P. Ttrahf'dron t969, 2.5. 4tl7-4t26;
Huheey, J. E. J. Org. Chm. 1971. J6. 204-205 .
.. Irving. H.; Williams, R. J . P. J. CMm. Soc. 1953, JJ92-3l10.
Hard ond Soft Acids -d 8a.s..
345
part from ligand field effects IChapter I I). A second observation is that certain ligands
form their most stable complexes with metal ions such as Ag . Hg2 . and PtH . but
other ligands seem to prefer ions such as AIH, TiH. and Co)+ ,47 Ligands and metal
ions were classified48 as belonging to type (a) or (b)4Y according to their preferential
bonding. Class (o) metal ions include those of alkali metals. alkaline earth metals. and
lighte.r transition metals in higher oxidation &ares such as TiH, c,J, FeH, Col+ and
the hydrogen ion, H+. Class (b) metal ions include those of the heavier transition
metals and those in lower oxidation states such as Cu Ag+. Hg , Hi. Pd2 +, and
According to their preferences toward either class {u) or class lb) metal ions,
ligands may be classified as type (o) or (b), respectively. Stability of these complexes
may be summarized as follows:
Tendency to tomple.r with

class (a) metal ions
Tendency tn cnmplu with

doss (b) metal ions
N>>P>As>Sb
0 >> S > Se > Te
F > Cl > Br> I
N P >As > Sb
0 << S < Se - Te
F < Cl < Br< I
For example, phosphines (R)P) and thioethers

have a much greater tendency to
coordinate with
Pd 2+ , and Pt2 , but ammonia, amines (R)N), water, and
lluoride ions prefer Be2 +, Ti4 +, and Co3 +. Such a classification has proved very useful
in accounting for and predicting the stability of coordination compounds.
Pearsons suggested the terms "hard" and "soft" to describe the members of
class (a) and (b). Thus a hard acid is a type (a) metal ion and a hard base is a ligand
such as ammonr or the fluoride ion. Conversely, a soft acid is a type (b} metal ion and
a soft base is a Jegand such as a phosphine or the iodide ion. A thorough discussion of
the factors operating in hard and soft interactions will be postponed temporarily, but it
may be noted now that the hard species, both acids and bases, tend to be small,
slightly polarizable species and that soft acids and bases tend to be larger and more
polarizable. Pearson sugge.s ted a simple rule (sometimes called Pearson's principle)
for predicting the stability of complexes formed between acids and bases: Hard acids
prt![er to bind to hard bases and soft acids prefer to bind to soft bases. It should be
noted that this statement is not an explanation or a theory, but a simple rule of thumb
which enables the user to predict qualitatively the relative stability of acid-base
adducts.
Hr.
dossmcation of
Acids and Bases as
Hard or Soft
In addition to the (a) and (b) species discussed above that provide the nucleus for a set
of hard and soft acids and bases, it is possible to classify any given acid or base as hard
or sofl by its apparent preference for hard or soft reactants. For example, a given
existence of isolated ions of high charge such as

in chemical systems is cneiJelically
unfaYOrable. NCYenheless. compues exisl wilh these elements in high formal oxM!alion states .
., Ahrtand, S. : Chan, J. : Oavics. N . R. Quarr.

Chtm. Stl<'. 1958. 11, 265-216. See olso
Schwarzcnbach, G . Expmtntio Suppl. 1956, $, 162
.. The (o) and (bl symbolism is arbilr.ll'y. Someeimes Jhe symbols A und 8 are used. Neilher shoukl be
confused wilh Jhe A and 8 subJt'oups of Ihe periodic table or A ard 8 as gmeric rq>resentalions of
acids a nd bases .
.., Only a limited
of examples of cl:lss {o) and (b) metal ions is pven here. A more complele
Usling is llf'OYided in Table 9.7.
" Pearson, R. G . J. Am. Chtm. Soc. 1963, 8.S, 3Sll-3S39.
346
9 Acid-Ba dtemistrr
base, B. may be classified as hard or soft by the behavior of the following

equilibrium:S2
(9.71)
In this competition between a hard acid (H+) and a soft acid (CH3 Hg), a hard base
will cause the reaction to go lO the left, but a soft base will cause the reaction to
proceed to the right.n The methylmercury cation is conveniem to use because it is a
typical soft acid and, being monovalent like the proton, simplifies the treatment of the
equilibria.
An important point to remember in considering the information in Table 9.7 is that
the terms hnrd and soft are relative, with no sharp dividing line between them. This is
illustrated in part by the third category. "borderline," for both acids and base.s. But
even within a group of hard or soft, not all will have equivalent hardness or softness.
Thus. although all alkali metal ions are hard. the larger. more polarizable cesium ion
will be somewhat softer than the lithium ion. Simi@rly, although nitrogen is usually
hard because of its small size, the prese.nce of polarizable substituents can affect its
behavior. Pyridine, for example. is sufficiently softer than ammonia to be considered
borderline.
Add-Base Strength
and Hardness and
Softness
Hardness and softness refer to special stability of hard-hard and soft-soft interactions
and should be carefully distinguished from inherent acid or base strength. For example, both OH- and F- are hard bases; yet the basic.ity of the hydroxide ion is about
roll times that of the fluoride ion . Similarly. both
and Et 3P may be considered
soft bases; however, the latter is 107 times as strong (toward C H3 Hg). It is possible
for a strong acid or base to displace a weaker one, even though this appears to violate
the principle of hard and soft acids and bases. For example. the stronger. softer base.
the sulfite ion. can displace the wealc, hard base. fluoride ion. from the hard acid. the
proton. H+ :
soj- +
HF
HSO)
(9.72)
Likewise the very strong. hard base. hydroxide ion, can displace the weaker soft
base, sulfite ion, from the soft at:id. methylmercury cation:
OW + CH 3 HgSO) ;::::::: CH 3Hg0H + Soi-
Kcq
10
(9.73)
In these cases the

of the bases (roj- > F-. Eq. 9.72: OH- >
Eq.
9.73). are sufficient to force these reactions to the right in spite of hard-soft considerations. Nevertheless, if a competitive siluation is set up in which both strength and
hardness-softness are considered, the hard-sofl rule works:
Kcq- lol
(9.74)
(9.75)
Jl
If tl'is equilibrium is studied in aqueous solucion. as ia usually lhe case, chc acids wiD oewr as
and H,o wich acldicional wruen or hydrution. For dam on equilibria or this type.
see Schwarunboch, G.; Schelenbcrg, M.
Chim. Acta t965, 48. 28.
n All interesling historical sidetiJht on chis type or soli-soli intcraclion is che orisin of the name
"mercaptan." a mm:ury capturer: Hj + 2RSH -
Ha<SR!:!
+ 2H+.
Hard and Soft Adds and Bases
Tal.le9.7
Hard and sofl ocicls and
.......
Hard ocicls
H+, 1..1-+, Na. K+(Rb+, Cs+)
Bel+,.Be(CH3J,, Mr. ci!. sil"(Ba2 ">

s2. uJ. ci!" . ad'. L.t?. nr. u<". uo::. Pu..
1t. zt, Hr'", Vd". Cr". cl'. MoO"'. WCf+. Mrr, Mr?. Fe'",
coJ+
BF3 , 801 , B(0Rl3
Af'. AI(CH3 ),. AICI,. AJH3 Gal+, In"'
C02 , RCO, NC", st. Sn....

NH'. RPO:. ROPO:, AsH
CH,Sr?"; (CHJ.,scr+
so1. RSO;.
Roso;
7
. -
". a . r'". 11+

HX (hydrogen bonding molerules)
Borderline ocick
Fe1 . c;d-, Njl, c.J. Zn2 +
Rhl+, lr', Rif. ()$l
B(CH1 ),, GaH,
R3C", C.H;. Srl", Pbz..
NO'".
sol
5b"'J,
Bi'+
pcf. J>r. Pf'
eu, Ag+, Au". Cd!+.
Hg2 . CH,Hg
BH1 , Ga(CH311 Ga03 GaBr3 , Gal 3, n: Tl(CH3}3
CH1 carbenes
'INtC:ceptors: trinitrobenzene, chloroanil. quinones. tetracyanoelhyle.ne. etc.

HO+, RO+, RS". RSe". Te. RTe
Br1 Br. lz. 1. lCN. etc.
0, Cl, Br,l. N, RO, R01
MO (metal atoms) and bulk metals
B.....
Hard hoses
NH1 RNH2 N!H
H1 0, OH-. r:;-, ROH, RO-. R10
CH3
PO!-. sd.-.
coo-.
No;.
F-<a->
Soft .......
H-
R-. C1H C6 f4. CN-. RNC. CO
SCN-, R3P, (ROhP, R3 As

R,S, RSH, RS", Sz{)j1-
.; J
. -
cro;
348
9 Acid-lase Otemislry
Table 9.8lists the strengths ol various bases toward the proton (H+) and the meth}'lmercury cation (CH3 Hg ). Bases such as the sulfide ion (51 - ) and triethylphosphine
(Et 3P) are very strong toward both the methylmercury ion and the proton. but about a
million times better toward the former; hence they are considered soft. The hydroxide
ion is a strong base toward both acids, but in this case about a million times better
toward the proton; hence it is hard. The aqueous fluoride ion. F - , is not a particularly
good base toward either acid but slightly better toward the proton as expected !Tom its
hard character.
The importance of both inherent acidity and a hard-soft factor is well shown by
the Irving-WiUiams series and some oxygen , nitrogen, and sulfur chelates (Fig. 9.5).
The Irving-Williams series of increasing stability from
to Cu2+ is a measure ol
increasing inherent acidity ol the metal (largely due to decreasing size). Superimposed
upon this is a hardness-softness factor in which the softer species coming later in the
series (greater number of d electrons, see page 350)
ligands S > N > 0 . The
harder alkaline earth and early transition metal ions (few or no d electrons) preferentially bind in the order 0 > N > S.
Symbiosis
As noted above, the hardness or softness ol an acidic or basic site is not an inherent
property of the particular atom at that site, but can be influenced by the substituent
atoms. The addition of soft, polariz.able substituents can soften an otherwise hard
center and the presence or electron-withdrawing substituents can reduce the softness
of a site. The ac.idic boron atom is borderline between hard and soft. Addition ol three
hard, electronegative fluorine atoms hardens the boron and makes it a hard Lewis
acid. Conversely. addition of three soft, electropositive
softens the boron
and makes it a soft Lewis acid. Examples of the difference in hardness of these two
boron acids are
R 2SBF3
R 1 0BH 3
+ R1 0--+
+ R1S--+
R1 0BF3 + R2S
(9.76)
+ R1 0
(9.77)
R1 SBH,
In a similar manner. the hard BF1 molecule will prefe.r to bond to another fluoride ion,
but the soft BH1 acid will prefer a softer hydride ion:"
BF 3
B1 H 6
+ F-
+ 2H-
- - BF;
(9.78)
--+ 2BH;
(9.79)
Therefore, the following competitive reaction will proceed to the right:
BF3 H- + BH 3F - - BF;
+ BH;
(9.80)
,. In a manna" analogous to I he IISIIAi trealmtnt clbalanciq redox cqUIUions. jt is necessary here to do

some careful "bookkeepina. Althol.wh thU il merely a fotm.Wsm, it is ncccs......-y to make cer1ain
thai the proper compamon is belq made. In the poe.wat
tile fonnalion ol BF, is formally
<:cn$idc:red 10 be 8' + JF". The thl"ec F- ions harden the sJ. The -tccous COI1\pllrUon is
s + JH- - BH,. 111 this cue !he S<!{l hydride ions solicn 1t1e s. One must be careful 10
dis&in&uisft between the small, hard pt'OIOn IH 1 and ltle tatae (r_ - 208 pon). soli hydride ion (H-).
"The simple BH, molecule does nol uis1 in appreciable quanlilies. but always dimtrizcs to S.H..
Sec Chapter 16.
Hard a nd Soft Acids a nd Ba ses
Table 9.8
Bmieity toward 1M proton
and methytm.rcvry cation
l.ialcing atom pK, (CH.Hg+) piG." {H)
Base
F-
a-
1.50
S.25
6.62
8.60
9.37
Cl
Br-
Br
x-
I
0
0
OHHro;-
sz-
so2-
NHJ
p-NH2C6H4SO)
PhzPC6H4SOi"
Elzl'CzH4 0H
EtJP
CN pK.
s.OJ
s
s
s
s
s
HO<;H4SseN-
2.85
-7.0
-9.0
-9.S
JS.7
6.79
14.2
9.S2
21.2
16.12
6.0S
8.11
10.90
7.60
2.60
9.1S
14.6
IS.O
14.1
N
N
p
p
p
-4
6.79
negative
9.42
3.06
-o
8.1
8.8
9.14
l<lSlCH,HaBV[CH,Hg l[sl
Joa{HBI/!WUBJ
II
Fig. 9.5 The lrviOigWilliams effect: The

staiJ;II!y inc:renses in the
,\
: \
, '
1
I
10
H,C - CH,
..
' l'IH,
s./
..
,,
,,
I
Ba
St
c.
Mn
Fe
Co
ffi
Cu
Zn
series Ba-Cu, decreases

wilh Zn. (From Sigel. H.;
McCormick, D. 8 . Ace.
Ru. 1970. J , 201.
Reproduced with
permission. I
349
350
9 Acid-law Chemistry
The isoelectronic fluorinated methanes behave in a similar manner;S6

(9.81)
has referred to this tende.n cy of fluoride ions to favor further coocdination

by a fourth fluoride (the same is true for hydrides) as "symbiosis." Although other
factors can work to oppose the symbiotic tendency , it has widespread effect in
inorganic chemistry and helps lo explain the tendency for compounds to be sym.
metrically substiluted rather than to have mixed substituents . We have seen (Chapter 5) that the electrostatic
ofC-P bonds (ionic resonance energy) will
be
in CF4 , and similar arguments can be made for maxi miring hard-hard or
soft-soft interactions.
Theorelical Basis of
Hardness a nd
Softness
Although the hard-soft rule is basically a prugmatic one allowing the prediction of
chemical properties, it is of interest to investigate the theoretical basis of the effect. In
this regard there is no complete unanimity among chemistS concerning the relative
importance of the various possible factors that might affect the strength of hard-hard
and soft-soft interactions. Indeed, it is probable that the various factors may have
differing importance depending upon the particular situation.
A simple explanation for hard- hard interactions would be to consider them to be
primarily electroswic or ionic interactions. Most of the typical hard acids and bases
are those that we might suppose to form ionic bonds such as u. Na. K ... r, and
OH- . Because the electrostatic or Madelung energy of an ion pair i.s inversely
proportional to the interatomic distance, the smaller the ions involved, the greater is
the attraction between the hard acid and base. Since an electrostatic explanation
cannot account for the apparent stability of soft-soft intemct ions (the Madelung
energy ofa pair of large ions should be relatively small), it has been suggested that the
predominant factor here is a covalent one. This would correlate well for tmnsition
metals, Ag. Hg. etc . since it is usually assumed that bonds such as Ag-CI are
considerably more covalent than the corresponding ones of the alkali metals. In this
regard the polarizing power and the polariubility of d electrons becomes important. It
has been pointed out that all reaUy soft acids are transition metals with six o r more d
electrons, with the d 10 configuration t Ag . Hg!) being extremely good.,. From this
effects in soft-soft interactions resemble in some ways
point of view the
the ideas of Fajuns (Chapter 4). alt hough there are notable differences.
Ele ctronegativity
In general,
having relatively hi&h elcctronegativities are hnrd am! those having
low electronegativities arc soft. In this regard it should be recalled that we are
considering ions and that alt hough Li. for example. has a low electronegativity. the
u ion has a rcl<uively high electronegativity resultins from the extremely high
second ioniution potential. In contrast. transition metals in low oxidation states
tCu... Ag +. etc.) have relatively low ioniution energies and low electronegativities.
The same may be said of hard and son bases. This relation between hardness and
and Hardness and

Softness
""Eqwtion 9.Ht is not mcan1 10 imply llwl A mixlure d

and
woukl
reac1 10 ronn ldr.ll!auomctl\aM :and methanr. ollhwch tbe f'Cktion wo"ld be 'xatltumit: if i1
ocaHTtd. In I his c:a.sc, as in mony others in chenoislly, kincric: considenuions (J;od of a suilable
mcch:lnisml ovaridc l'avor.>bic lhennodynamic:s.
C. K. iltcwtl. CMm. t964. J. t201-1202.
<a Alwland. S.
Bo11Jilt11 t&orlml 1966. /, 2117.
Hard and Soft Acid aad Ia..
351
elcctronegativity helps explain the fuct that the trifluoromethyl group is considerably
harder than the methyl group and boron trifluoride is harder than borane.
definition of electronegativity involves two paramRecall that the
eters. a, the first derivative of the ionization energy- electron affinity curve. and b. the
second derivative (see page 186). The a term is identical with the original Mulliken
electronegativity, and the b term is the inverse of the charge capacity of an atom or
group. It appears that the association between elec tronegntivity and hardness actually
refers to the b paramete.r . but the values of a and b for elements tend to parallel each
other. hence the similarity. It was early suggested that since the b parameter is the
inverse of the charge capacity. hard atoms will have high values of b. and sort atoms
will have smaller values_n . S9Thus fluorine not only forms a hard anion (note the very
high value of b in Table S.6) b!!! it likewise hardens the trilluoromethyl group by
contributing to a higher b value for it than for methyl.
Recently Parr and PearsonM have used the b parameter to investigate the hard and
sort properties of metal ions and ligands . They have termed this the ubsol11te hardness
in comparison to the
a parameter which they call absolute electronegativity. They provide strong arguments for the use of the absolute hardness
parameter in treating hard-soft acid-base (HSAB) interact ions.
Almost from the beginning of HSAB t.h eory. attention has been directed to
frontier orbituls.61 These are the highest occupied moluular orbital (HOMO) and
the lowest unoccupied molecular orbital (LUMO). According to Koopmans' theorem,
the energy of the HOMO should represent the ionization energy and the LUMO the
electron affinity for a closed-shell species. These orbitals are thus involved in the
electronegativity and HSAB relationships just discussed: Hard species have a large
HOMO-LUMO gap whereas soft species have a smaii83P. The presence of low-lying
unoccupied MOs capable of mixilljl with the ground state accounts fo r the polarizability of soft atoms and, indeed. Politz.er has shown a close correfation between
atomic polarizabilities and the b parameter...z Such mutual polarizabilityaJJows distortion of electron clouds to reduce repulsion. In addition. for polarizable SpeCies
synergistically coupled u donation and 11 backbonding will be enhanced."'
The idea of equating hard- hard interactions with electrostatics has probably been
overemphasized. It is natural. since a typical hnrd- hard interaction is Li+F-. But the
bonds. The Li- F
isoelcctronic series Li-F, Be-0, 8-N. C-C 111/ form
bond is the
since it is a resonllnce hybrid of Li F - ..... li-F. Some
calculations based on electronegativity theory 01nd a simple bonding model suggested
that in LiF nbout one-fourth of the bond energy comes from covalent bonding. onehair from ionic bonding. and one-fourth from the transfer of electron density from the
less electronegative lithium utom to the more electronegative fluorine ntom ."" The
latter corresponds roughly to Pauling's ionic resonance e.nergy.
,. Huheey. J . E. : Evans, R. S. J . l mJ#'I/. N11cl. Clrrm. ti)')O. Jl, lll'I- J90.
.. P:IIT. R. G.; Pc:arson. R. G. J. Am . Cll..,._ Sr..-. t983. /OS , 7512-7516; Pe:.non. R. G. J . Clwm.
t987. 64. S6t-.567. lniliaUy 1hc l':>rr- P<UiliOO penmc1er W'Jll ) rbilrnrily defined "" 'I
t1 - AJ/2. This r=lls in 'I - b/2. II should lllso he no1e.S 1hn11he P:IIT-Pwi",,In numbcrure 1101 , in
for
in 1hcir volcncc
10 aiUiiun mll>l be IJ$Cd in lhcir :applic:Dtion.
Klopmnn, G. J . Am . drrm. Soc. 1964,86. t463-t469: t9611, 90, 22l- D4.
Ol Potiw:r. P. J. Ctwm. Phys. 1987, 86. IO'n- t07l.
r.l Bad<bondirc in metal c<JIT1Illcxc:s is cfiscusscd in Chup1cr 11 . For a dar diSICUWon of HOMOs.
LUMOs, and HSAB. see Peanon. R. G. J . Am . Clrrm. StiC. 19115, t07. 61!01..()806; 1986. 108.
and Foolnote 60.
"'See Footnote 38 and the auociated discuuion ol wonc cov:atenl bondl,. by fluoride
352
9 Acicl-8ase Che111is1ry
Larger atoms do not have the advantllgt of good overlap for s1rong covalency, rlor
short interatomic distances for strong electrostatic interactions. In fact. if one investigates a typical HSAB reaction in the gas phase when all of the energies are. known, we
find
l:t.H = - 397 kJ mol- 1 (9.82)

Soli-hard
Hard-sofl
Hard- hard
Sort-son
The HSAB rule works and the reaction is exothermic as written. If we look at the
individual heats or atomization o( the species (from bond energies, Appendix E) we
find BeF2 .. + 1264; HgF2 .. +536; Bel 2 +578;
+291 kJ mol- 1 . The
driving force in Eq . 9.82 is almost entirely the strong bonding in the hard-hard
interaction.
One advantage that softer acids and bases generally tic have is the ability 10
1rbond. This is made possible by large numbers of electrons in d oroitals on the met.aJs
and empty, low-tying acceptor orbitals on the ligands. Once again. "bigger" is not
necessarily "better": Once an atom is large enough, that is. has n = 3, it will have
available d orbitals. Sulfur and phosphoru.s arc exemplars of soft-atom behavior. They
are much better at binding sol\ metals than are their larger congeners such as selenium, arsenic, tellurium, and antimony. This is for the same reason we have seen
before: Long 1r bonds arc not very strong just as long u bonds arc not very strong, but
the effect is even more pronounced because of the sideways overlap lo form 1r bonds.
The premier sol\ Ji.tand and 1r bonder is carbon monoxide which has low-lying 1T*
acceptor orbitals and which has the advantage of small size lo oblain good overlap.
Both the HSAB principle and the ,.E8 -C,.C8 sys1em were proposed and developed in the 1960s. Insofar as the HSAB principle employs ideas of electrostatic and
covalent bonding to account for hardness and softness. it was natural to attempt a
correlation with the Eand C parameters. 1lle early 1970s showed repeated attempts to
correlate the two ideas, prove one superior to the other. or to improve their theoretical
bases. M For example, both Drago and Pearson have discussed 1he possible quantifiCll
tion of the HSAB principle along the fines of the - C system. but have come to
diametrically opposed conclusions. Drago and coworkers have even suggested that
the HSAB model is no longer tenable.
Part of the difficulties encountered in comparing these two approache.s results
from the d ifferent ways in which they are used. The -C approach treats the interaction of only two species al a time: to the extent that the nonpolar solvenls used in lhese
studies minimize solvation effects, the results are
to gas-phase proton
affinities. In contrast. the HSAB principle is usually applied to exchange or competition reactions oC the son:
A 1B 1 +
;::::::::;;: A 1 B2 + A2 B 1
(9.83)
We have already seen that in the gas phase the stability of all metal
follows the
order F- > Cl- > Br- > 1- , contrary to the simplest possible interpretation of the
HSAB rule. Perhaps the rule should be restaJed as follows: Son acids prefer to bond to
soft bases wMn hard acids are preferentially bondins to hard bases. Although the
HSAB rule works in the gas phase. by far its greatest usefulness lies in the interpreta-
R. S.: Kabler. R. A. lttorf(. Clwm. t9'71. II, 1144-314.1. Dnao. R. S. lbiJ. t97l. 12.
2211-2212. Purson. R. G. /ftCKf(. Clwm. t971. 11.3146. Dnao. ll. S . J. Clo,m.
1974. .11.
300-307.
Hard and Salt Aeids and Basu
353
lion of complexes in aqueous solution. These ions will always be hydrated though this
may not be explic.itly stated. Under these circumstances, it is somewhat surprising
thut the HSAB rule works as well as it does .
McDaniel and coworkers66 have presented a graphical means of portraying some
of the ideas discussed in this chapter. For the reaction of hard and soft acids and bases
A.B. +
---+ AB
+ A,B.
(9.84)
it can be shown that the enthalpy change for this reaction, t:.H,. can be related to the
affinities of the bases for the two acids as shown in Fig. 9.6. If the affinities for a hard
acid (e.g . H .. } and a softer acid (e.g. CHjl are plotted and lines of unit slope are
drawn through them. l:J.H, for the reaction can be measured by the distance between
the lines in either the x or y direction. Furthermore, if two bases were 10 fall on the
same line in Fig. 9.6, they would be equally soft. If the line for a given base lies above
and to the left or that for another. the first base is softer and the second is harder.
Finally. since strength is related to the magnitude of acid-base interoctions. the
further a given base lies from the origin, the stronger it is.
Some typical anionic bases are plotted with their proton affinilie.s and their methyl
cation affinities in Fig. 9.7. The solid line was drown by the original investigators as a
least squares tit of all of their data. The dashed line was added for this discussion. and
it is arbitrarily drawn through F- and OH- (the archetypical hardest bases) with unit
slope (see Fig 9.6). Hard bases lie close to the dashed line, soft bases lie further away
from it. The reader is urged to lind analogous pairs, such as,- and r, SH- andOH-,
CN - and NH2. and interpret their positions on lhis graph in terms of inherent
strength. hardness , and softness.
Slaley and coworkers67 !]ave provided direct measurement of HSA 8 effects in
gas-phase dissociation energies between transition metals (where the principle has
fig. 9.6 McDaniel
illustrating HSAB param
eters. d, is the difference in
affinity of tWO bases, B,
and
s . for the hard acid
A . The reaction enthalpy.
Ml,.. of Eq. 9.84 is given by

the haizontal
(or
vertical distance) between
the two lines of unit Slope.

(Courtesy of D. H.
McDaniel.)
Amnlly ror hard acJds, e.s., Ah or tr
""McDaniel, 0. H . The Univenity of Cincinnati. pet>On3! communic:alion, J97S.

' Kappes. M. M.: Sioley. R. H. J. Am. Clw!m. Sac. 1982.104. 1813, t819. Joncs. R. W.; Staley. R. H.
Ibid. 1982. 104. 2296. J. Phy&. Cht:m. 1?82.
1387.
Procctl offinicy (kc:ol moc- 1)
Fig. 9.7 Me1hyt cation affinity vs. proton affinily of a series of anionic bases of varying
hardness. The solid line is a least-squares fit of the data drawn by the oriGinal investigaton.
The dashed line has been arbitrarily drawn through F- and OH- with unit slope (see Fig.
9.6). Hard bases lie dose to the dashed line, soft bases lie fur1her away from il. [From
Br:wman. J. 1.; Han. C.-C. J . Am. Clt<'m. Soc. 1!188, 110. 5612. Reproduced wirh
permission.!
-2
-t
4D(Mn -LI Ita! mol- 1
354
Fig. 9.8 Comparison of relative lipnd dissociatiOn energies for Mn and Co. Zero pOinls
for the scales have been arbi1rarity chosen. Nolc lhat for Jhe nJ/1 ligands, MeSH. HCN.
EtSH. and Me,S. the dala poinls lie above and 1o the ten of those for lhe oxygen bases. This
indicates relatively st.-onga- hard-hard bondq (0-Mnl or son-son bonding ts-eoJ. or
both. (Modified from Jones. R. W.; Staley, R. H. J. Phys. Clr<'m. 1982.86. 1387. Reproduced
with permission.)
Problems
355
always proved most useful) and various ligands. both hard and soft. As expected. cu
(dt") is significantly softer than co (d8 ) , which in tum is softer than Mn Cdi. A
and Mn is given in Fig. 9.8. There is the expected
comparison of the results for
correlation oC dissociation energies for a large series o( oxygen bases, the variation
along the line resuhing from differences in substituents, hybridization. electronegativity, etc. However, as soon as the hard oxygen bases are replaced by softer
bases such as MeSH, EtSH .
and HCN, a new line is generated with the softer
Co+ ion showing ca. 30 kJ rnol - 1 greater dissociation energies. The reader is referred
to the original articles that contain far more data and interesting ligures than can be
presented here. In summary. all o( these data are consistent with the HSAB effect
acting in the absence of complicating solvent effect s to stabilize either hard-hurd
interactions. or soft-soft interactions, or both.
In summary, acid-base chemistry is conceptually rather simple, but the multiplicity of factors involved makes its treatment somewhat involved. Until more unifying concepts are developed. as they undoubtedly will be. it will be nec,e ssary to apply
to each problem that is encountered the ideas, rules, and (when available) the parameters applicable to it.
eo
Problems
9.1
Use the Lewis ddlnition of acids and b3$e$ 10 explain the eumples gi.-en l'or 1he
BtJ!nSted-Lowry, Lux-Rood, and SOlvent system definitions (Eqs. 9. 1-9.4, 9.5-9.1.
9.9-9.36).
9.2
Use lhe cencralizt<l definition ol acid' and bl!Se$ to ellpl:sin the eumples &iven for the
Lux-Flood. solvtnl system. nn.l Lewis definitions ( Eqs. 9. 1-9.4.
9.5-9.8. 9.9-9.36; 9.37-9.40).
9.J
Which would yoo expect to be a better Lewis acid, sO, Of' B(CH,h? Explain.
9.4 The order of acidity of boron halides is BF1 < BCt,
< BBr,.
Is there anythirt unexpected
in this o rder? Sugges1 possible: expbmuions.

9.5 l'tot the acidity pnramelers. " from
9. 1 vs. the pK values in T blc 9.3 for those
me1als I hat occur in both 1ables. Interpret your plot.
9 .6
B-s1rain can occur in

10 lower I heir b.ic:ity. Will B.<lrJin inhibi1 or cnholnce the
behavior of bornnes?
acidic
9.7
Predict which way tho folluwinc rc:oc:tions will GO (left or righll in I hell"" pholse:
HI + NaF - HF + Nal
All,+ 3NaF- AIF, + 3Nal

Cul 1 + 2CuF
Tif4 + 2'Til1
CoF1 + HgBr1
CuF1 + 2Cul
-
Til4
+ 21iF1
CoBr1 + Hgf'1
9.8
Calculate the v:.Jues for the proton affinities ol1hc halide anions shown in Table 9.S rrom a
Bom-Haber thermochemical cycle and values for ionization ener;ies. electron affinities.
and bond energies.
9.9
Usina Eq. 9.61. alcubte the pro1on allinilies oltbe rollowini bases: NH,. CH,NH!.
(CH11:N H. ICH,bN, py, H,O. (CH,):O. H,S. (CH,)zS, and tCH,)lSO
b. Compare your answers wi1h experimental values as (liven in Table 9.S. Whictl ccm
pOUnds show lhe
dilrerences between !J.H,..., and 0 H....? Discuss possible
reasons for the <lill'trertcell.
cr=est
356
9 Acid-aa.. Chemistry
9.10 a.
Do you expect dimelhylsulfoxide. (CH1):SO. to bind to H thrOIJB}I the sulfur or )he

oxygen atom'/ Support your prediction wi1h numbers.
b. calculate I he a.ffiniliu of the follow ina

H20 . NH,. CH,N H2 , tCH1hNH, tCH 1),N
for t rimethy!staMYI cntion, (CH,),Sn :
for correlatina ncid-base phenomenA Me obtained in ps-phasc:

experiments rather than in solution. Dis russ factors present in solution. especially in polar
SO!wnts. lhot make soiiJtion dala SUipcCI .
9. 11 In scneral, the bcSI data
9 . 1Z In contraSI 10 the gcncr.>Jization made In Problem !U I there is reason to believe the

solulion daJn for CH1()(CH!). N H1 may be more indiutive of inherenl bMicity than the
gas-phase work. CAn you SUgtSI reason? (Hint: Consider the possibilities for hydrogen
bonding.)O"
9. 13 a. Estimate the :IPpt'OXimate pK. of phO><phoric and arsenic acids.
b. Refine your answer by decidil'll whelhcr H1P04 or H1As04 is stronger.

9. 14 Phosphorous acid can
as either of two taulomcrs.
II
I
or H-P-OH
OH
From lhc pK. of phosphorous acid (1.8) ossian a struciUre to the fonn of phosphorous acid
in aquc:ou.s solulion. The pK. of
acid. H1PO:. is 2.00. Assitn a reasonable strucrure. (Sec Chapkr 18.)
9.15 In Fig. 9. 1. c:o..Jd you have assianed the pc:alts if t he: tcaend had not?
9.16 Tbc disc:U$Sions of basicity of amidcs on
)}4 and lo42 are b:L'Icd upon the catbonyt
beins the: basic site. It is at<o possible that the QITijdc nit rogen atom could act as a
base. What expc:rima>t31 work could you suggest 10 dclerminc w hich atom is the most
basic sile!
9.17 If you d id net answer Problem 5. 14 When you read Chapte<' 5, do so now.
9. 18 Using Fig. 9.6, cxpl:lin wh y H2S is considered softer t han H!O even thouah it binds more
Jighlly to the: har d acid H .
9.19 Comptclc and balance Jhe followins t'lualions. identil'yins the acids aflll the bases .
. so,+ K,o-.
b. MgO + At,O, c. AI,O, + Na,O-.
d.
CaO + P.O.,-
e. SiO,
+ K,, + AI:O, + MgO-
9.20 If you did not answer Problem 6.26 when you read Chapter 6, do so now.
9.ZI Potassium metal rcac1s with graphile to fonn an intercalation compound
C,.K. WiD this ma1erbl act as an acidic or basic Calalyst?"'
oz-.
9.22 PrediCI t he order of proton affinities (Of' lhc: followin& bases: N R,. g>-. NF,.
NH,.
O H- . NO,, N'-. Pick any pair of bases from this series and explain why you decided that
one was stronaer llu1n the: other.
tot
Lo"". P.; Collen. R. 8.: ntt. R. W. J. Am. CNm. 5. 1968. 90. 1455.
D. .:
KiJioulh. J. M. J. Chnrt. S.. Clomt. Co'"""'" 19'7f. 9Jl-9J4.
PYoblems
357
!1.23 CakutaJe tile enmalpies for oil ol the possible I: I react.i ons between the
H CH:.
PF,. and CF,CH,OH. and t he bases OH" . NH,. (CH,),P. and Cl" . You may check some
of your answcn uaainst Table 9.S. How accunte lll'e your calculations?
9.24 Examine Fig. 9.2 and provide a rationale for the relationship therein.
!1.25 Most frequen tly the chan< i n frequency of the cnrbonyl group upon coordination to a
Lewis acid is stated in terms of bond order. DevelOp such an argument.
9.26
a. We team in organic chemistry that C0 H,NH 3 and C,H,N ore weaker blUes than N H,,
but Table 9.5 indicmcs otherwise. Discuss, inctudinll the Important molecular anributes
of each molecule. (Hint: See RO " , page 3441.
b. Water is a weak acid. but most hydroellrbonsare usually considered to have vinuall!' no
acidity whatsoever. How.:ver. in the Ill'S phase c.H,CH, is 10" stronger OS an acid than
H,O. Discuss the pM1icular
propenics that cause the gas-phose values 10 be
different from soiWion data and to differ so much between these t wo species.
9.27 Reconcile the values ol the proton affinities o( pyridine (9S3 kJ mol" ') and arrunonia (87! kJ
mol"'> with the araument on Pille 343 concerning the relationship between pKh and
electnaneg:uivily. The latter argument seems to
with the "convention..t wisdom" raJ her
than the discussion in this chapter. Critiei:u:.
ao
9.28 Usillll :o Bom-Habcr cycle. c.le:lrly show aU o( the terms that one should evaluate ;,
considerin& the
involved in
the competition (as &ivcn by the enthalpy of reaction):
BH.(sl
+ B'(&l 2!!._.
B(B)
+ B'H"(S)
(9.85)
into solution:
OH(aq)
+ B"(:>q)
+ B'H(aq)
(9.16)
Once you have your Born-Huber <liag-m llr-wn. return to Prublem '1.21\
to clarify your anliWC:rs.10
> if it helps
9.29 Dioxygen.
is not a very aood lignd. but it l\ fairly ofl. Hemoglobin contains Fe,.
which is only oC borderline softness.
a. Look at the structure ol the heme &rOUP onll SU88CSt how the ir on in heme is 5oflencd.
b. Carbon monoxille is poisonous bccuuse it
more lightly to the hemoglobin in red
Noud cells than .toes dioxygen. Why docs clll'bon
out<ompc.tc
as a
ligand?
9.JO Whut is t.h c significunce uf lhc twu line shuwn in Fi;. 9.7? How .to they ilitrer? What arc
the softest basn shown in t his
9.31 How is it possible for the noble guses tO have exothermic proton affinities, indicating the
formation of X-H cht miclll hmuh"!
9.32. Presumably. in the cas phase I F,O, has the :<arne structure as Cl F 30,, but the s tructure of
tile solid is a bit of a surprise. Suggest possibilities. (Hint: Remember chat the current
chapter deals with Lewis acid-base interactions.)
9.33 a. Acid rain is defined as any prccipiwtion with pH
< $ .6. Wily S.6; why not 7.0"!
b. Some ill effects ol acid rain come not frum the low pH. per se, but from the toxicity oC
metals ions. Explain.
10
Arnett. E. M. J . O.tm. Est.c. 1915,62, 383.
358
9 Acid-lase Cltemistry
9.34 Explain wllul effect acid rain would have on I he condition or cac:fl oflhe following and why:
a. The Taj Mahal. at Agra. India

b. A limeslone bam ncar Antietam BatUefield. Maryland. dating from the Ovil War
c. The Karyalides. the Acropolis. Athens. Greece
d. The abilily of an aquruic snail to (()nn its shell in a lake in the Adirondack Mounlains
e. The asbestosshingled roof on the house of one of the authors in College Parte. Maryland
r.
The integrily of the copper eaves-troughs and downspouling on that house
r;. The integrity of 1he brick siding of that house

Ia. The growlh of the azaleas planted along lhe IOundation of that house
l The integrity of the aluminum siding on a nelahbor's hOUse

j. The slate roof on another neighbor' s house
k. The longevity of galvanized steel fencing in the neiiJ>borhood
9.35 Throughout this chapter. the ftuoride ion is referred 10 as a strong base. yet good.
iiiUstrnlive examples are seemingly not common. Suggest a few such examples. Why are
there not mo" simple examples ofF"' actil'll! as a sarong base or nucteophile? Suuest ways
of making slrong F- bases."
11
Schw.. ingcr. R.; lJnk. R.; llliclc. 0 .: Rouer. H.; Honcf1. 0 .; Umbach. H H.; Mannie. F.
Clwm. Int. 4, Enk>l. t991. JO, 1372-137S.
Chapter
10
Chemistry in Aqueous
and Nonaqueous Solvents
I
Almost all of the reactions tha.t the practici11g inorganic chemist observes in the
laboratory take place in solution. Although water is the best-known solvent. it is not
the only one of importance to the chemist. The organic chemist often uses nonpolar
solvents such as carbon tetrachloride and benzene to dissolve nonpolar compounds.
These are also of interest to the inorganic chemist and. in addition. polar solvents such
as liquid ammonia. sulfuric acid. glacial acetic acid. sulfur dioxide. and various
nonmetal halides have been studied extensively. The study of solution chemistry is
intimately connected with acid-base theory. and the separation of this material into a
separate chapter is merely a matter of convenience. For example. nonaqueous solvents are often interpreted in terms of the solvent system concept. the formation of
solvates involve acid-base interactions. and even redox reactions may be included
within the Usanovich definition of acid-base reactions.
There are several physical properties of a solvent that are of importance in
determining its behavior. Two of the most important from a pragmatic point of view
are the melling and boiling points. These determine the liquid range and hence the
potential range of chemical operations. More fundamental is the permittivity (dielectric constant). A high permittivity is necessary if solutions of ionic substances are
to form readily. Coulombic attractions between ions are inversely proponionalto the
permittivity of the medium:
qq-
= -41TrE
(10.1)
where E is the permittivity. In water. for example. the attraction between two ions is
only slightly greater than 1% of the attraction between the same two ions in the
absence of the solvent:
(10.2)
where EQ is the permittivity of a vacuum. Solvents with high permittivities will tend to
be water-like in their ability to dissolve salts.
359
360
lOCMmis lry in Aqueo and Nonaqueous Solv""b
Toble10.1
Physical
.....,...m.. of water
100 oc
o-c
Boiling point
Freezing point
Density
Pennittivity (dielcdric constant)
1.00 g em- 3 (4
81.7E (18
Specific conductance
4 X
Viscosity
Ion product constant
1.008 x lo- mof L-z (25 "C)
J(J'"a n-l em- 1 (18 OC)
1.01 g em- s- (20 q
Water
Water will be discussed only briefty here but a summary of its physical properties is
give.n in Table 10.1 fur comparison with the nonaqueous solvents to follow. One
notable property is the very high permittivity which makes it a good solvent for ionic
and polar compounds. The solvating properties of water and some of the related
effects have been discussed in Chapter 8. Electrochemical reactions in water are
discussed on pages 378-381.
Nonaqueous
Allhough many nonaqueous solvent systems have been studied. the discussion here
will be limited to a few representative solvents: ammonia, a basic solvent; sulfuric
acid, an acidic solvent; and bromine triftuoride, un aprotic solvent. In addition a short
discussion of the chemistry taking place in solutions of molten salts is included.
Solvents
Ammonia
Ammonia has probably been studied more extensively than any other nonaqueous
solvent. Its physical properties resemble those of water exceptthatthe permillivity is
considerably smaDer (Table 10.2). The lower dielectric constant results in a ge.nerally
decreased ability to dissolve ionic compounds, especiaRy those containing highly
charged ions (e.g., carbonates, sulfates, and phosphates are practically insoluble). In
some cases the solubility is higher than might be expected on the basis of t he
permittivity alone. In these cases there is a stabilizing interaction between the solute
and the ammonia. One type of interaction is betwee.n certain melal ions such as
and Zn2 + and the ammonia molecule, which acts as a ligand to form stable
ammine complexes . A second type is between the polarizing and polarizable ammonia
molecule and polarizable solute molecules or ions. Ammonia may thus be a beuer
solvent than water toward nonpolar molecules. Ionic compounds containing large,
polarizable ions such as iodide and thiocyaoote also are quite soluble.
Table 10.2
l'toysic.. properties
of ammonia
Boiling point
1
Freezing point
DensitY
.,, < ,.
Permittivity (dielectric const&rlt)
Specific
.,. ,- _
Viscosity'
lon
. '
GJ!i' .- ;;
t
-33.38 "C
-77.7 "C
0 .725 g cmJ ( - 70 "C)
26.7*o ( - 60 "C)
n-o an-1
an-
.-(- 33 o
27
I . X 10- 11
0 .254 g
s, I
x 10- rr.oi L- z
Nonaqos Solvents
361
Precipitation reactions take place in ammonia just as they do in water. Because of

the differences in solubility between the two solvents, the results may be considerably
different. As an example, consider the p.-ecipitation of silver chloride in aqueous
solution:
KCI + AgN0 3
--+
AgCI! + KN0 3
(10.3)
In ammonia solution the direction of the reaction is reversed so that:
AgCI + KN0 3
--+
KCI! + AgN03
(10.4)
Ammonia undergoes autoionization with the formation of ammonium and amide

ions:
2NH3
.,......:::
NHt + NHi
(10.5)
Neutralization reactions can be run that parallel those in water:
KNH 2 + NH 41
--+
Kl + 2NH 3
(10.6)
Furthermore. amphoteric behavior resulting from complex formation with excess

amide also parallels that in water:
cxcusOH-
Zn2 + + 20H-
-+
Zn2+ + 2NH2
-+
Zn(NH1 )2 !
_ _ . Zn(OH>!-
(10.7)
uecssNH;
---+
(10.8)
2
Zn(NH2)-
All acids that behave as strong acids in wate.r reoct completely with ammonia (are
leveled) to form ammonium ions:
HC104 + NH3
--+
NHt + CIO;
HN03 + NH3 - - + NHt + NO;
(10.9)
(10.10)
In addition, some acids which

as weak acids in water (with pKu up to about 12)
react completely with ammonia and hence are strong acids in this solvent:
(10.11)
Furthermore, molecules that show no acidic behavior at all in water may behave as
weak acids in ammonia:
(10.1 2)
The basic solvent ammonia levels all species showing significant acidic te.ndencies and
enhances the acidity of very weakly acidic species.
Most species that would be considered bases in water are either insoluble or
behave as weak bases in ammonia. Extremely strong bases, however, may be leveled
to the amide ion and behave as strong bases:
H- +NH 3
--+
NH) + H 1 l
oz- + NH3 - - + NHi + OH-
(10.13)
(10.14)
Solvolysis reactions are well known in ammonia, and again many reoctions
parallel those in water. For example, the solvolysis and disproportionation of halogens
may be illustrated by
362
10 Cha ...iatry in AqHous and Nonaqueous Solvenb
02 + 2H 2 0 -
HOCI + H,o
+ CI -
(lo.IS)
Cil + 2NHl ---+ NH1Cl + NH; +a-
(10.16)
Since it is more basic than water, ammonia can cause the disproportionation of sulfur:
SS1
+ l6NH 3
4S4 N -
+ 12NH:
(10.17)
The hexasultide ion is in dissociative equilibrium: 1
s!- =:; 2S)
(10.18)
The Sj" ion is responsible for the deep blue color of these solutions C-'m ., 610 nm).
This ion is also responsible for the color of sulfur dissolved in chloride mells (see
below) and in the aluminosilicate known as ultramarine (see Chapter 16). Many
nonmetal halides behave as acid halides in solvolysis reactions:
+ JH,o + 3CI+ 30-
OPCI 3 + 6H 1 0 -
OP(OH),
OPCI1 + 6NH 3
OP(NH 1 ), + JNHt
--
(10.19)
(10.201
The resemblence of these two reactions and the structural resemblance between
and phosphoramide (OP(NHll3J has led some people to
phosphoric acid
use the term ammono acid"' to describe the Iauer.
In a manner analogous to that uud for water, a pH scale can be set up for
ammonia; pH = 0 (I M NH;); pH - 13 ((NHtl - [NH!J). neutrality; pH
26 (I M
NH2 ). Likewise oxidation-reduction potentials may be obtained. based on the hydrogen electrode (see page 379):
EO - 0
(10.211
In summary. the chemistry of ammonia solutions is remarkably par.sllel to that of

aqueous solutions. The principal differences are in the increased basicity of ummonia
and its reduced dielectric constant. The latter not only reduces the solubility of ionic
materials. it promotes the formation of ion pairs and ion clusters. Hence even strong
acids. bases. and salls are highly associated.
Solutions of Metals
in Ammonia
If a small piece of an alkali metal is dropped into a Dewar Rask containing liquefied
ammonia. the solution immediately assumes an intense deep blue color. If more alkali
metal is dissolved in the ami1Ulnia . eventually a puint is reached whe.re a
phase separates and floats on the blue solution.! Further addition of alkali
metal resulls in the gradual conversion of blue solution to bronze solution until the
former disappears. Evaporation of the ammonia from the bronze solution allows
one to recover the alkali metal unchanged.' This unusual behavior has fascinated
chemists since its discovery in 1864. Complete agreement on the theoretical interpretation of experimental observations made on these solutions has not been achieved.
solulion is comptu wioto runbtr equilibria and disp-oponionolion reaction. Sec Dubois. 1'.:
1988, 17. t883-t190: t989. 28. 19S-100.
2 Caicmo IPIJC8I'> oo be an
. Alohoueh the sotu1ion dlanaes rrom blue lo bronz.e with
COf1Cltnll"lllicln. a
sysocm is never obusincd.
J
be very earefuloo ududc w:>lcr and 01"" mlllcriols wtlich ...,I react wish lhc a1Jc.a1i
me1:11 Dad lhm preven1 she
or Ibe solution.
1 The
Letieur, J. 1'.: l.epouOK. G. IMrR
.. Solvents
363
but the following somewhat simplified discussion will indicate the most popular
interpretations.
The blue solution is characterized by ( I) its color, which is independent or the
metal involved: (2) its density, which is very similar to that of pure ammonia; (l) its
conductivity. which is in the range of elecrrolytes dissolved in ammonia: and (4) its
paramagnetism, indicating unpaired electrons, and its electron paramagnetic resonance g.factor. which is very close to that of the free electron. This has been
interpreted as indicating that in dilute solution, alkali metals dissociate to form alkali
metal cations and solvated electrons:
(10.22)
The dissociation into cation and anion accoums for the electrolytic conductivity. The
solution contains a very large number or unpaired electrons. hence the paramagnetism, and the g value indicates thntlhe interaction between solvent and electrons is
rather weak. It is common to talk or the electron existing in a cavity in the ammonia,
loosely solvated by the surrounding molecules. The blue color is a result or a broad
absorption peak that has a maximum at about ISOO nm. This peak results from an
absorption or photons by the electron as it is excited to a higher energy level. but not
all workers are in agreement as to the nature of the excited state.
The very dilute solutions of alkali maals in ammonia thus come dose to presenting the c.h emist with the hypothetical "ultimate" base. the free electron (Chapter 9).
As might be expected, such solutions are metastable, and when
the electron is "leveled" to the amide ion:
(10.2.3)
The bronze solutions have the foDowing chamcteristics: (I) a bronze color with a
definite metallic luster; (2) very low densities; ()) conductivities in the range of metals:
and (4) magnetic susceptibilities similar to those of pure metals. AQ of these properties
are consistent with a model de.scribing the solution as a "dilute metal" or an " alloy"
in which the electrons behave essentiaUy as in a metal, but the metal atoms have been
moved apart (compared with the pure metal) by interspersed molecules or ammonia.
The nature of these two phase.s helps to throw light on the metal-nonmetal
transition. For example there has been much speculation that hy<.lroge.n molecules at
sufficiently high pressure, such as those occurring on the plonet Jupiter. might undergo
a transition to an "alkali metal." The fUndamental transition is one or a dramatic
change or the van der Wuals interactions of H2 molecules into metallic cohesion.s
Solutions of alkali metals in ammonio have been the best studied, but other metals
and other solvents give similar results. The alkaline earth metals except be.ryUium
form similar solutions readily, but upon evaporation a solid "ammoniate,"
.
is formed. Lanthanide elements with stable + 2 oxidation slates (europium. yuerbium)
also form solutions. Cathodic reduction of solutions of aluminum iodide, beryllium
chloride, and tetraalkylammonium halides yields blue solutions, presumably containing AJ'+ , Je-; BeZ+, 2e-; and R.N ... e- respect ively. Other solvents such as various
amines, ethers, and hexamethylphosphoramide have been investigated and show
some propensity to form this type of solution. Although none does so as readily as
ammonia, stabilization or the cation by complexation results in typical blue solutions
Edwords, P. P. Adv.
t-r. CMm. RtllliMm. 1982. lJ. 1lS..I8S.
'Edwards. P. P.; SO...o, M. J. J. Am, Ciwm. S. 1'8t.IOJ.2967. See also FoolnokllinC!Iaptcr7.
364
10Chemistry ia ACIMOus and NonaqMous Solvefth
in ethers.6 The solvated electron is known even in aqueous solution. but it has a very
short (-to-1 s) lifetime.
These solutions of electrons are not mere laboratory curiosities. In addition to
being strong bases. they are also good one-electron reducing agents. For example,
pure samples of alkali metal superoxides may be readily prepared in these solutions:
M+ + e-
+ Ol -
M+ + Oi
(10.24)
The superoxide ion is further reducible to peroxide:

M+
+ e- + 02 _... M+ +
Oi-
(10.25)
Some metal complexes may also be forced into unusual oxidation states:
[Pt(NH1)J1 + 2M+
Mo(C0)6
+ 2e- -
[Pt(NH,)4 l
+ 6Na+ + 6e- + M+ + e- -
M+ + Au-
Au
+ 2M+
Na.[Mo(C0)4)
(10.26)
(10.27)
(10.28)
The chemistry of metal electrides has been extensively studied and although the
formulation M e- is undoubtedly the best, most chemists have the aiJ-tocH!uman
emotion of feeling more secure in their science if they have something more tangible
than solutions and equaJions on paper. Therefore the isolation and structural charac.
terization of cesium electride, (Cs(ligand)Je-. as single crystals was welcome. indeed.7 The crystals are dark blue with a single absorption maximum at ISOO nm. have
no likely anions present (the empirical formula is 1: I. Cs:ligand. with a trace orlithium
impurity, an artifuct of the synthetic technique), and are most readily formulated as a
complex of cesium electride.
Sulfuric Acid
, ...1.10.3
!'hysical properties of
sulfuric acid
The physical properties of sulfuric acid are listed in Table 10.3. The dielectric constant
is even higher than that of water, making it a good solvent for ionic substances and
leading to extensive autoioniZDtion. The hiah viscosity, some 2.5 times that of water,
introduces experimental difficulties: Solutes are slow to dissolve and slow to
crystallize. It is also difficult to remove adhering solvent from crystallized materials.
Furthermore. solvent that has not drained from prepared crystllls is not readily
removed by evaporation because of the very low vapor pressure of sulfuric acid.
Boiling point
Freezing point
Density
Pennittivity (dielectric constanl)
Specific conduc:tance
Viscosity _
Jon product constant
JOO
-c (with decomposition)
10.371 -c
1.83 8 cm-J (2.5 "C)
l l<lo (20 "C)
1.04 x 10- 1 n-em- (2.5 "C)

24..54 8
(20 'C)
2.1 x Jo- mol' L-z (2.5 <c>
em- s-
Dye. J . L : Odladter. M. G.: Nicety. V. A. J. Am. Clltm. Su<-. 19'10. 92. $226-S228.
7 lssa. 0.: Dye. J . L J . Am.
$. 1912. UU, )781 . For I he c:rystaiSINCIUfe of this compoond,
see 0Jap1er t2, f"OS. 12.5Gb.
Sol,_
365
Autoionization of sulfuric acid results in the for mation of the hydrogen sulliue
(bisulfate) ion and a solvated proton:
2H1 S04
H 3 SO,t
+ HSO;
(!0..29)
As expected, a solution of potassium hydrogen sulfate is a strong base and may be

titrated with a solution containing H 3SO,t ions. Such a titration may readily be
followed condooometrically with a minimum in conductivity at the neutralization
point.
Another method that has proved extremely useful in obtaining information about
the nature of solutes in sulfuric acid solution is the measurement of freez.ing poiru
depressions. The freezing point constant (lc) for sulfuric acid is 6. 12 kg c mot-. For
ideal solutions, the depression of the freez.ing point is given by
liT=
(10.30)
km11
where m is the stoichiometric molality and 11 is the number of particles fOrmed when
one molecule of solute dissolves in sulfuric acid. For example, ethanol reacts with
sulfuric acid as follows:
c!H 5 0H + 2H1 S04
+ HSO; + H,o
__.
11
(10.31)
It is found thai aD species that are basic in water are also basic in sulfuric acid:
OH- + 2H:zS04
NH 3 + H 1 SO..
--o
2HSO; + H 3 0
HSO;
+ NH.t
(JD.32)
11-2
(JO.Jl)
II
Likewise, water behaves as a base in sulfuric acid:

11
()0..34)
Am ides. such as urea. which are nonelectrolytes in water and acids in ammonia accept
protons from sulfuric acid:
I
NH1 C(O}NH. + H1so. -
Hso;
+ NH1C(O}NH;
11
uo.Js>
Acetic acid is a weak acid in aqueous solution and nitric acid a strong acid, but both
behave as bases in sulfuric acid!
+ H1 SO -
Hso; +
HN03 + 2H 2 S O - 2HSO; +No;+ H30
v=2
(J0.36)
(J0.37)
Sulfuric acid is a very acidic medium, and so almost all chemical species which react
upon solution do so with the formation of hydrogen sulfate ions and are bases.
Because of the extreme tendency of the H2S04 molecule to donate protons, molecules
exhibiting basic tendencies will be leveled to HSO; .
The concen!nlion ol ions it 11 a miri....,m Ihe ncUiralizotlon

point, but
Ihe ccnduc:tivily dqocncls on viscosity as weD (wllicll chanacs with compooillon),lhe
absoluJe minimum c:onduclivlty does no1 OCCUf' CJUICtly when [H,SO; I [HSO;[. The slillC
dill'erenc:e is no1
in pnctlte, howe-tu.
'lllis Sl:llemcnJ is net quile
a.cc
366
10Chemistry in Aq. .ous and Nonaqueous Solvents
Perchloric acid is one of the strongest acids known, but in sulfuric acid it is
practic:llly a nonelectrolyte, behaving as a very weak acid:
HCI04 + HzS04
H 3 S01"
+ C104
(10.38)
One of the few substances found to behave as an acid in sulfuric acid is disulfuric
(pyrosulfuric) acid. It is formed from sulfur trioxide and sulfuric acid:
sol + H2so. H2S10 ,
+ Htso.
HzS201
(10.39)
H 3SO;
(10.40)
+ HS20 7
An exceptionally strong acid in sulfuric acid is hydrogen tetrakis(hydrogensulfato)borate, HB(HS04 ) 4 The compound has not been prepared and isolated in pore form,
but solutions of it may be prepared in sulfuric acid:
H 3 B03 + 6H 2S04
B{HSOJ4 + JH30+ + 2HSO;
v = 6
(10.41)
Addition of S03 removes the H10+ and HSO; ions:
B(HSO.);
+ 3H3 0 + + 2HSO; + JS03
Hlso:
+ B(HSOJ; + 4Hlso.
(10.42)
Some very strong acids have been termed "superacids.''9 They consist of simple
very strong Brj!nsted acids such as di.s ulfuric acid, very strong Lewis acids such as
antimony pentalluoride, or combinations of the two. One of the most interesting is
"magic acid," a solution of antimony pe.ntalluoride in ftuorosulfonic acid. It acquired
its name when a postdoctoral fellow happened to drop a small piece of a Christmas
candle (following a lab party) into such a solution: The paraffin candle dissolved! 1'he
wax, composed of long-chain alkanes. would not be expected to be soluble in such a
very polar solvent. Furthennore, a 1H NMR specuum of the sample showed a sharp
singlet characteristic of the t-butyl cation, indicating much cleavage a nd rearrangement. This type of reaction is most simply shown by the reaction with neopentane:
(10 .43)
CH
H1 C-t-CH1 +
CH1
1
[
CH
H1C - t -
CH 4
(CH 1 ) 3c + CH
CH 3
(10.44)
The strongest known superacid is a solution of antimony pentalluoride in hydrogen

lluoride:o
(10.45)
' This oermo"'"'oedin ohe oille aapapcrby Hall. N. F.:Conant.J. B. J . Am. Ch#m. Sue. 1927.49.
3047-3061. but modem worit on superacids dales from ohe 1960s and t970s: Gillespie. R. J.: Peel. T .
E.Atlv. P/ry. Org. Clwm. 1972.9. 1-24; Olah.G. A. Angrw. C*rm.lnt. Ed. Engl. 1973, /2, t73- 212.
Olah. G . A.; Prakash. G. K. S .; Sommer, J . Suptrocitls; Wiley: New Yorit. t98S.
oo Gillespie. R. J .; Liane. J . J . Am. Chrm. S. 1988. 110.

Eq. t0.4S is simplified rordilute
solutions. A3 ohe conc.c:n1raoion of SbF, increllsu. polynuoro:unimonaoe specie$ are formed wilh
complex equilibria.
N011aqueoU1
Solvents
367
Even such unlikely bases as Xe, H2 0 2 , Br!, and C02 have been shown to accepl H ..
ions from superac.ids, though perhaps only to a small extent. There is no evidence that
Ar, 0 2 , or N 2 become protonated.
Summary of
Protonic Solvents
Despite certain differences, the three protonic solvents discussed above (water, ammonia, and sulfuric acid) share a similarity in their acid-base behavior. All are
autoionizing, with the ionization taking place through the transfer of a proton from one
molecule of solvent to another with the formation of a solvated proton (Brfilnsted acid,
solvent system acid) and a deprotonated anion (Brjilnsted and Lewis base, solvent
system base). The inherent acidities and basicities of these three solvents differ.
however, and so their tendencies to protonate or deprownate solutes differ. It is
possible to list solvenJs in ocder of their inherent acidity oc basicity. Water is obviously less acidic than sulfuric acid but more so than ammonia. Glacial acetic acid lies
between water and sulfuric acid in acidity. Figure 10.1 graphically illustrates the
relative acidities and basicities of four solvents. together with various acid-base
conjugate pairs. They are listed in order of the pK0 in water. In an ideal aqueous
solution the pH of an equimolar mixture of conjugates is given by the pK.,, and similar
acidity scales may be used in other solvents. The pK., is thus a rough estimate of
acidity in solvents other than water. Any given acid is stronger than the acids listed
above it and, conversely. any base is stronger than the bases below it. All species that
lie within the extremes of a particular solvent behave ns weak electrolytes in that
solvent and form weakly acidic oc weakly basic solutions. All species that lie beyond
the enclosed range are leveled by the solvent.
An example may serve to illustrate the information that may be oblained from
Fig. 10. 1. Consider acetic acid. In water. acetic acid behaves as an ac.i d or, to be moce
precise, an equimolar mixture of acetic acid and an acetate salt will have a pH of4.74.
If acetic acid is added to sulfuric acid. it will behave as a base and be leveled to
CH3C(OH>;. the acetic acidium ion, and HSO; (cf. Eq. 10.36; note the equilibrium
lying at a bout - 9 on the scale in Fig. 10. 1).
If dissolved in ammonia. acetic acid will behave ns a strong acid and be leveled to
NH; and CH 1Coo- (cf. Eq. 10.11; note equilibrium lying atabout4.7 on the scale in
Fig. 10. 1). The different behavior of acetic acid as a base (sulfuric acid), a strong acid
(ammonia). or a weak acid (water) depends upon the acidity or basicity of the solvent.
The ..equilibrium boxes" for the solvents (Fig. 10.1) indicate the range over
which ()ifferenti8.1ion occurs; outside the range of a particular solvent, all species are
leveled. For example, water can differentiate species (i.e . they are weak acids and
bases) with pK..'s from about 0 to 14 (such as acetic acid). Ammonia, on the other
hand, behaves the same toward acetic ac.i d and sulfuric acid because both lie below
the differentiating limit of -12. The extent of these ranges is determined by the
autoionization constanl of the solvent (e .g . -14 units foe water). The acid-base
behavior of several species discussed previously may be seen to correlate with
Fig. 10. 1.11
A complete discussion of relative acidities and basicities would be 10o extensive
to be covered here. Nevertheless it is possible to summarize the behavior of acids and
bases as involving (I) the inherent acidity-basicity of the solvent , (2) the inherent
acidity- basicity of the solute, and (3) the interaction of solute and solvent to form an
" For a more extensive discussion of Jhe use of ronjqote acid-bue charts like F'111. 10.1, see
T,.ptow, R. S. J.
Educ. 1986.61. 9-941.
368
10 CltemiotTy in AqiHiovs and NanaqMous Solve nts
Conjucate acich ond bcscl<.

Acids
Ph 1CH
40
3.5
-H"
+H"
B4K1
Ph,c-
NH,
NHi
PhNH1
PhNW
-2S
- 20
"
1!
au
30
- 15
"'
ll
2S
NSCCH,
NSCCHi
20
CH,CCH,
CH,cCH;
..,.... IS
Nl-f,CNH 1
NHlCNW
"'
-tO
'!i
.!i
'0
II
.i
li
'5
"
".2
II
CH_.COOH
+OH HS04
II
NH,CNH,
H ) 6
>
-s i!
0
?,
;-
.!i
'ii
.,
.....
:f
CH1coo
PhNH2
so1o
!g
c
:2
;;
OH ..
H 10
..,c
S>
I[
10
II
I!
!I
<
Ill
II
H;o
I}
-}
20
CH_,COOH!
H 2so.
CH1COOH
HSO.i
HCIO,
C10.i
HS,Q;
- tO
H_.so:
HBtH$0)
BIHSO,I.i
ffi
Acelic
ncid
2S
Sutruric
DCid
or
Fis- 10.1 Relative acidity and basicity solvenu;. Solvents

solutes are li.sted from lop
to bottom in order of decre.asing basicity and increasing acidity. Solutes are listed in order oC
clecreasing pK,. a. delermined in water. Some values of pK. are esairruued. In ideal aqueous
soiUJions. equimolar mixtures of an add and ils coJ1iugate
will have a pH equal to I he
pK. The range of acidity and ba.sicity over wflic.h a par1icutar solvent is dilferenliatin; is
shown at lhe righl. All acids lying below and all bases lying above the enclosed box will be
leveled 10 lhe characterislic cation and anion the solvenl. The arrows involving CH,COOH
and NH, illuSirate lhe facl that an acid will readay donate a proton to a base above it and to
the right.
or
No..oqoeous Solve..ts
369
equilibrium (the "weak" case, differentiation) o r

to go essentially to
completion (the "strong" case. leveled). Finally. it must be recalled that only solvents
of high dielectric constants can support electrolytic solutions. Solvents of low dielectric constants will result in weak electrolytes irrespective of acidity or basicity
arguments.
Aprotic Solvents
..-
Thus fur. the solvents discussed have had one feature in common with water. namely.
the presence of a transferable hydrogen and the formation of onium ions. In this
section we shall look brieRy at solvents which do not ionize in this way. These may be
conveniently classified into three groups. The first group consis ts of solvents such as
carbon tetrachloride and cyclohexane which are nonpolar, essentially nonsolvating,
and do not undergo
These arc useful when it is desired that the solvent
play a minim11m role in the chemistry being studied, for example, in the determination
of E and C parameters discussed in the previous chapte.r .
The second group consists of those solvents that are polar. yet do not ionize.
Some examples of solvents of this type are acetonitrile, CH 3C==N: dimethylacetamide, CH 3C(O)N(CHY2; dimethyl sulfoxide (dmso).
and sulfur
dioxide. SOz. Although these solvents do not ionize to a sianificant extent, they are
good coordinating solvents because of their polarity. The polarity ranses from low
(S01) to extremely high (dmso). Most are
solvents tending to coonlinate
with cations and other acidic centers:
CoBr1 + 6dmso -
[CO{dmsol,.f+ + 2Br
SbCI, + CH 3C=o=N
(10.46)
(10.47)
--+
A few. the nonmetal mtilles and halides. can behave as acceptor solvents. reacting
with anions and other basic centers:
(IUS)
This group of solvents ranges from the limiting case of a nonpolar solvent
(Group I) to an autoionizing solvent (Group Ill . see below). Within this range a wide
variety of reactivity is obtained. Gutmann I! has defined the dont" n11mber (ON) as a
measure of the basicity or donor ability of a solvent . It is defined as the negative
enthalpy of reaction of a base with the Lewis acid antimony pentuchloride, SbCI3 :
B + SbO, -
BSbCI,
DNShCJ,s - t.H
(10.49)
These donor numbers provide an interesting c.o mparison of the relative donor abilities of the vurious solvents (Table 10.4). ranaing from the practically nonpolar 1.2dichloroethane to the highly polar hexamethylphosphoramide.
Note,
however, that there is no exact correllltion between donor number and permittivity.
Some so lven1s with relatively high permittivities such as nitromethane and propylene
carbonate (/En
38.6 and 65 .1) may be very poor donors (ON
2.7 and IS. I).
Conversely, the best donors do not always have high permittivities: pyridine ION =
33. 1. e/c0 ,. 12.3) and diethyf ether (ON 19.2. t/a '"' 4.3). This should serve to
remind us that solubility is not merely an electrostatic inten1ction but that solvation
also involves the ability to form covalent donor bonds. Note that pyridine may be
considened to be a relatively soft base (Chapter 9). Gutmann has extended the concept
370
lOChemioll'y in Aqueou1 and Nonaqueouo Solvents
Table 10.4
Solvent
Donor numb (ON).

acceptor number (AN). and
rolativ pannittMty
(dielectrie constan!,
of
selected solvents
DN
Acetic acid
Acelone
Acc!Onitrile
Antimony pentachloride
Bemene
AN
S2.9
17.0
14.1
0.1
Olloroform
Dichloromethane
Diethyl ether
Dimethylacetamide
Dimethylformamide (dmt)
Dimethylsulfoxide (dmso)
Dioxane
Hexamethylphosphoric triamide (hmpa)
Nitromethane
Phosphorus
Propylene carbonate
Pyridine (py)
Tetrahydrofuran
Trifluoroacetic acid
Trilloorosulfonic acid
Water
..
19.2
27.3
24.0
29.8
14.8
38.8
2.7
11.7
IS. I
33. 1
20.0
18
- i2.S
'19.3
100.0
8.2
8.6
23.1
20.4
3.9
13.6
16.0
19.3
10.8
10.6
20.S
14.2
8.0
105.3
129.1
54.8
l*o
6.2
20.7
36
2..3
2.2
4.8
4.3
37.8
36.7
4S
'2.2
38.6
6S.I
12.3
7.3
81.7
The ratio /o is more convenient tO use than the value of the pcnniltivity in
absolule unitS.
"From Gutmonn. V. ChimJo, 1971.J/, I; TM Donor-Acup10r App<ooch to
/ntu octioru; Plenum: New Vorl<. 1918. Used with permission.
to include an acceptor number (AN). that measures the electrophilic behavior of a
solvent (Table 10.4).1l Drago has criticized the donor-number concept because it
does not so far enough in accounting for differences in hardness and softness (or
electrostatic and covalent differences}. By limiting the evaluation of donor numbers to
a single acid (SbCI5). the donor-number system in effect presents only half of the
information available from the ,.0 + C,.C 8 four-parameter equation.
The third group of solvents consists of those that are highly polar and autoionizing. They are usually highly reactive and are difficult to keep pure because they react
with traces of moisture and other contaminants. Some even react slowly with silica
containers or dissolve e lectrodes of gold and platinum. An example of one of the more
reactive of these solvents is bromine trifluoride. Nonfluoride salts, such as oxides,
carbonates, nitrates, iodates, and other halides, are fluorinated:
BrFi
Ge02
2BrF; +
PBr,
..!!:!.
BrF;
NOCI
l l Gutmann.
lA
+ SbF6
Sb20,
V.
Drago. R. S. /norg.
+
+
(10.50)
(10.51)
Pf6
(10.52)
BrF.4
(10.S3)
Arto 1976.21. 661-670; Chimio 1977. Jl. 1-7.

1990. 29. 1379-1332.
Nonaqueous Solvents
371
Fluoride salts dissolve unchanged except for fluoride ion transfer to form conducting
solutions:
K+ + BrF;
(10.54)
Ag + Brf;
(10.55)
SbFs
BrFi + SbF;
(10.56)
SnF4
2BrFi
AgF
BrF,
(10.57)
These solutions can be considered acids or bases by analogy to the presumed autoionization of BrF3: s
2BrF3
.....=
BrFi + BrF;
(10.58)
Reactions IO.SO 10 IO.S2. 10.56. and 10.57 above may be considered to form acid
solutions (BrFi ion formed) and reactions IO.S3 to JO.S5 may be considered to form
basic solutions (BrF; ions formed). Acid solutions may be readily titrated by bases:
(BrF2 )SbF6 + AgBrF4
AgSbF6 + 2BrFJ
(10.59)
Such reactions may be followed conveniently by measuring the conductivity of the

solution: A minimum occurs at the I: I endpoint. Solutions of SnF4 behave as dibasic
acids:
(10.60)
with minimum conductivities corresponding to I :2 mole ratios.

A similar, although less reactive , aprolic solvent is phosphorus oxychloride
(phosphoryl chloride). A tremendous amount of worlt on the properties of this solvent
has been done by Gutmann and coworlters.t6 They have interpreted their results in
solvent system terms based on the supposed autoionization:
OPCI3
OPar + Cl-
(10.61)
or the more general solvated forms:

(m
+ n)OPCI 3
+ [CI(OPCI3).,r
(lo.62)
It is extremely difficult to measure this autoionization because contamination with

traces of water yiekls conducting solutions which may be described approximately as:
(10.63)
If autoionization does occur, the ion product, [OPCiiiiCJ-1. is equal to or less than
S X 10- 14
Salts which dissolve in phosphorus oxychloride to yield solutions with high
chloride ion concentrations are considered bases:
(10.64)
(lo.6S)
IS This exl)<ession foc the 311loion!uuion of BrF3 Is based on lhe concluctivity of pure BrFJ and the
c:harac:taiz.otion of the BrF; salls such :as KBrF . The evidence for Brft is wealter. Further
support for this formulation is obtained from the 103 syst<m where X-ray evidence for ICt;" and
IC4 has been obtained.
06 Gutmann. V.
Chmmry in NonAqueous Solutions: Springer: New York. 1968.
372
lOChemislry in Aqueous and NOflaq,..ous Solvents
Most molecular chlorides behave as acids:

(10.66)
(10.67)
As might be expected. basic solutions may be titrated with acidic solutions and the
neutralization followed by conductometric, potentiometric, photometric. and similar
methods. Some metal and nonmetal chlorides are amphoteric in phosphorus
oxychloride:
K+
+a +
AI03
SbCI, + AIC1 3
OfC"I,
--+
OPCI,
--+
K+
+ AICI_;
AICI; + SbCI;
(10.68)
(10.69)
A table of relative chloride ion donor and acceptor abilities can be establishedt7 from
equilibrium and displacement reactions (Table IO.S). As expected. good donors are
generaUy poor acceptors and vice versa with but few exceptions (e.g . HgCI2) .
There has been some controversy in the literature over the proper interpretation
of reactions in solvents such as phosphorus oxychloride. Drago and coworkerstB have
sugge.sted the "coordination model .. as an alternative to the solvent system approach .
They have stressed the errors incurred when the solvent system concept has been
pushed funher than warranted by the facts. In addition, they have pointed out that
iron!lll) chloride dissolves in triethyl phosphate with the formation of tetrachloro-
Table 10.5
Relative chloride ion donor

and acceplcM" abilities
Chloride ion donon
IR.NJO
KO
AICI 3
Tia.
PC I,
ZnCt2
BCI3
SnCI.
AICJ:
SbC13
17 The ordering of this
tist is not invariant: Some or the compounds listed have very similar donor and
acceptor abiUties and exchange pbc:es depending IJil(ln the naJ...e of the Olhcr ions in soMion. This
is to be expected in a SCllvent or rclaJively low puminivily
a 13.9) where ion paic formatK>n
wal be irnponant and Jhc nature of the counterion can a!"cct the
of a dllori<le addu<:t.
,. Medt. D. W. ; 0rll80. R. S. J . Am. Clwm. Soc. 1961. BJ. 4322-432.5. Drago. R. S .; Purcel, K. F. In
Solvrnt Sysums; Wadcfinaton. T. C Ed.; Aca6en)ic: New York, t965: pp 211-Z.St .
Nonaqueous Solvents
373
ferrate(IIJ ) ions. FeCI;. just as in phosphorus oxychloride. In triethyl phosphate,

however. the solvent
behave as a chloride ion donor and so a reaction such as
Eq. 10.66 is not applicable. In triethyl phosphate the chloride ion transfer must take
place from one FcCJ1 tnolecule to another with the formation of a cationic iron( Ill)
species:
2FeC11
MOo,
-
[FeCI!{OP(OEtlJnl + FeC14
(10.70)
Drago and cowor1cers argue that in view of the similarity in physical and chemi
cal properties between phosphorus oxychloride, OPCI1 , and triethyl phosphate,
OP(OEtJ,. it is probable that the formation of Fea; in phosphorus oxychloride
proceeds by a reaction similar to Eq. 10.70.
2FcCI3
[Fe02(0POJ].]
FeQ;
(10.71)
They argue that the similar coordinating ability of these phosphoryl (-P-O) solvents (and to a lesser extent their dielectric
is more important than their
chemical differences (supposed autoionization and chloride ion transfer in phosphorus
oxychloride).
Gutmannt9 has rejoined that the dichloroiron(lll) ion . [FeCI2 (solvcntlt. is 110t
found in
solutions in phosphorus oxychloride but only in concentrated solutions
or those to which a strong acid such as SbCI5 has been added. In such cases the
chloride donor ability of the solvent has been exceeded and chloride ions are abstr:acted from the iron(lll) chloride. This point wus made earlier:!U by the observation
that the controversy is at least partly a semantic one. The only "characteristic
property" of the solvo-cations and solvo-anions in the solvent system autoionization
is that they urr the .ftrnngest ucids und bu.fi!S tltut cun exist in tltut purtkulur Stllwmt
witlwut beinx /evl!il!d. In triethyl phosphate (a nonleveling solvent) the dichloroiron( lll} ion is perfectly stable. In phosphorous oKychloridc a mechanism for leveling
exists. namely:
cto.n>
This equilibrium wi lie to the right iC the dichloroiron(lll) ion is a stronger acid than
the dichlorophosphoryl ion and to the left if the acid strengths are reversed. The
important point is that neither the solvent system approach nor the coordination
model can. a priori. predict the nature of the equilibrium in Eq. 10.72. To make this
prediction, one must tum to the generalized acid-base definition given above together
with some knowledge of the relative elect ron densities on the cenlrlll
in FeCI!
The essence of the acidity of iron( Ill) chloride lies in its tripositive ion of
and
small radius and high charge. which is compensated only in part by three
coordinated chloride ions and which seeks elsewhere for electron dcnsit y to reduce its
positive chatacter. It is thus an acid irrespective of the solvent chosen and will accept
the strongest base available to it. If the basicity of the phosphoryl group is sufficient
(as it must of necessity be in tricthyl
or in phosphorus oxychloride if the
chloride ion concentration is too low), then the iron( II I} chloride is less acidic than if it
can abstract a chloride ion (possible only in phosphorus oxychloride).
"'Out....,.,. V. Coordlmti411
in N11n-AqtHot18 Su/Miim11;
rercrcnces .........
10 Hubeey. J. E. J. '""'I
Clvm. 1"1. l4. 1011-IOtl.
Spri.lcer.
Yotlt, 1968. ond
374
10 Chemistry in Aqueous and NonaqMo Solvents
Mo lten Solts
The chemistry of molten salts as nonaqueous solvent systems is one that has developed extensively from the 1960s till the present. and only a brief survey can be given
here. The most obvious difference when compared with the chemistry of aqueous
solutio ns are the strongly bonded and stable nature of the solvent. a concomitant
resistance to destruction of the solvent by vigorous reactions. and higher concentrations of various specie.s , particularly coordinating anions . than can be obtained in
saturated solutions in water.
Solve nt Pro p e rties
On the basis of the structure of the liquid. molten salts can be conveniently classified
into two groups although there is no distinct boundary between the two. The first
consists of compounds such as the alkali halides that ;sre bonded chiefty by ionic
forces. On melting, very little change takes place in these materials. The coordination
of the ions tends to drop from six in the crystal to about tbur in the melt and the longrange order found in the crystal is destroyed: but a local order, each cation surrounded
by anions, etc., is still present. These fused salts are all very good electrolytes because
of the presence of large numbers of ions. They behave normally with respect to
cryoscopy and this is a useful means of study. The number of ions, v, may be
determined in these systems just as in the sulfuric acid .system {page 365). For
example, if sodium chloride is the solvent, "KF - 2, "BFt "' 3. etc. One
point is that a salt with a common ion behaves somewhat anomalously in that the
common ion does not behave as a foreign particle" and vis correspondingly lower.
In sodium chloride solutions, "NF I.
The second group consists of compounds in whK;h covalent bonding is important.
These compounds tend to melt with the formation of discrete molecules although
autoionization may occur. For example. the mercury( II) halides ionize as follows:
HgX
+ HgXj
(10.73)
This is analogous to the aprotic halide solvents discussed in the previous sect ion.
Acidic solutions may be prepared by increasing the concentration of HgX+ anti basic
solutions by increasing the concentration of HgXJ :
+ HgX1
KX + HgX 2
Hg(CIOh
2 HgX
+ 2CI0i
(10.741
+ HgX)
(10.75)
and neutralization react ions occur on mixing the two:

HgX+
+ CIO; + K + +
HgXj -
2HgX 2
+ K + CIOi
( 10.76)
If aluminum chloride is added to an alkali metal chloride rneh. an alkali metal

tetrachloroaluminate forms:
2{Mcn +
2M+ + 2AICI;
(IO.n)
The tetrachloroaluminate ion undergoes autoionization

2AIO;
AI1 CI;
+ a-
Kc 4
1.06 x 10- 7
(10.78)
and one can clearly relate basicity to the concentration or the chloride ion. At 17S +c
the neutral melt has [AI1 0;) ICI-1 3.26 x
Manda pCI scale can be set up
with a neutral point of 3.S. BasK: solutions have lower values of pCI (a saturated
solution of NaO has pCI 1.1) and acidic solutions (made by lidding excess A11CIJ
to-
Malte11 Salb
have higher vulues. The pCI can be monitored electrochemically with

electrode.21
Room-Temperature
Mol..n Sa lts
:10
375
aluminum
Although the tenn " molten salts" cor\iures up images of very high-temperature fused
systems. some salts are liquid at or near room temperature. For
if alkylpyridinium chlorides are added to aluminum chloride, the resultant compounds are
very similar to the alkali metal tetrachloroaluminates, but they are often liquids:n
(10.79)
The chemistry in these melts is very similar to that in MAICI except that it can be
carried on at about 25 c instead of 11S "C!
One problem with chloroaluminate melts is that aluminum chloride and most
transition metal chlorides (cf. Eqs. 10.99 to 10. 101) are hygtoscopic. and even if very
carefully handled will hydrolyz.e from any moisture in the atmosphere:
(AIC4r +
+ l HCI
+ (AICIJ-
--+
mat!- ;:= [TtOCJJz-
(10.80)
(10.81)
Such impurities are, of course. a problem whenever careful mensurements are atlempted. It has been foundn thai phosgene quanlitatively removes the oxide
impurities
[1iCI,J2 - + C02
(10.82)
(N bOCIJ- + OCCI2--+ (Nbqr + CO:
(10.83)
(Ti0CIJ1 - + OCCI1
--+
and this has proved a useful way to keep the systems anhydrous.
Although the chloroaluminates are the best known room-temperature molten

salts, there are several other interesting systems. For example. if one mixes the
crystalline solids triethylammonium chloride and copper(I ) chloride. an endothermic
reaction takes place to form a light green oil. The most reasonable reaction is the
coordination of :1 second chloride ion to the copper(() ionlA
(EtJNH ICI + CuCI -
(Et, NH)(CuCI:I
(10.84)
to form the dichlorocuprate(l) ion. The source of the low melting point seems lobe the
foUowing equilibria:
:o Chum. H. L.;O..Ier}'Olln&. R. A. In /01tic Liquids; Inmon, 0 .;

York. 198t;
L.oven.. 0 . G Eds.: Plaoum: New
""Sec Hussey. C. L. AJ. Multn Suit CJo,m. t 913. J. 185. Qalo, R. 1.; Osuryouna. R. A. In Molun
Suit Tch11iqurs; Lovctina. 0 . G.; Gale. R. J Eds.; Plenum: New Yorlt. 1983; Vol. I, pp SS-78.
Sun. 1-W.; Ward, E. H.; Hussey. C. l.. /'""II Chm. 1917, 16. 4l09-4lt I.
Por1afield. W. W.; Yoke. J. T. In /fiOffi'Jnlt:
wltlt Unusul Ptop.nln; KinQ. R. 8 .
Ed. ; Advances in Cloemlttty 00; Amctic:on Chemic:aJ Socic1y: Wcshin&ton. DC. t976: Oollper 10.
Hussey, C. H. Adv. Mo/Jm Solt Clo, m. 1913, J, t8S.
376
10 C...111istry in Aqueous aad Nonaqueous Solvents
+ cua
[Cu1 a,]-
2[CuCJ2]-
[Cu1c1, r
+a-
(CuCI1] 1 -
(eua 2
[ Cucl2] -
( IO.SS)
+ c i-
(10.86)
(10.87)
Evidence for these equilibria comes from the Raman spectra, which show an
absorption peak (or unresolved peaks), probably attributable to Cu2Cij'. Addition or
CuCI or CJ- causes this peak to increase or decrease as expected by the above
equilibria. The system thus probably contains at least four anionic species, and the
"impurities" account for the de.pression or the melting point. In accordance with this
interpretation is the fact that the materiul is oily and never forms a c.rystallinc solid
with a true freezing point, but congeals to a glass at about 0 c.
Of interest is the use or this system as bot h solvent and reactant in a voltaic cell. If
two platinum gauze electrodes are immersed in liquid chlorocuprates and a polential is
applied. the cell begins charging. At less than 1% of lUll charge. the potential stabilizes
at O.SS V and remains at that value until the cell is fully charaed. The half-reactions for
charging are
eua;-
+ e-
--+
cu
+ 2a+ c-
CuCI2 __...
(10.88)
(10.89)
A.llowing the reactions to proceed spontaneously (reverse or Eqs. 10.88 and 10.89)
produces O.SS V with low currentllow. The chief difficulty with the cell is the fact that
is soluble in the melt. It thus diffuses and allows the cell to decay through direct
reaction of the elc:ctXle materials:
CuCI1 + Cu + 2CI- -
2Cu0i
(10.901
The fact that the solvent can be both oxidized and reduced is an asset in the above
reactions, but it is a handicap when the system is used merely as a solvent. For
example. the chlorocuprate solvent must be handled in the absence of air to prevent
oxidation. Some solutes cannot be studied. Even so gentle an oxidizing agent as FeO,
oxidizes the solvent:
(10.91)
Unreactivity of
Molten Salts
Many reactions that cannot take place in nqueous solutions because or the reactivity
of water may be performed readily in molten salts. Both chlorine and Huorine react
with water (the latter vigorously). and so the use of these oxidiz.ing agents in aqueous
solution produces hydrogen halides. etc . in addilion to the desired oxidation products. The use of the appropriate molten halide obviates this difficulty. Even more
important is the use of molten halides in the preparation of these halogens:
-mr.,
l F! + 4H2 + KF
NaCI ....,,..,.,.., !CI + Na

2
(ID.92)
(10.93)
The latter reaction is also important in the commercial production of sodium, which.
like the halogens, is too reactive to coexist with water.
The reactions in Eqs. 10.92 and 10.93 are typical of the many impoc1llnt industrial
processes involving high-temperature molten salts. Other examples are the production
Molleft Salh
377
of magnesium and aluminum and the removal of silica impurities (in a blast furnace,
for example) by a high-temperaiUre acid-base reaction:
Si01
Gangue
Solutions of Metals
+ CaO
Flm
(10-94)
CaSi0 3
Slag
One of the most interesting aspects of molten salt chemistry is the readiness with
which metals dissolve. For example, the alkali halides dissolve large amounts of the
corresponding alkali metal, and some systems (e.g., cesium in cesium halides) are
completely miscible at all temperatures above the melting point. On the other hand,
the halides ofzinc , lead, and tin dissolve such small amounts of the corresponding free
metal that special analytical techniques must be devised in order to estimate the
concentration accurately.
At one time solutions of metals in their molten salts were thought to be colloidal in
nature. but this has been shown not to be true . However, no completely satisfactory
theory has been advanced to account for all the properties of these solutions. One
hypothesis involves reduction of the cation of the molten salt to a lower oxidation
state. For ellample, the solution of mercury in mercuric chloride undoubtedly involves
reduction:
(10.95)
and mercury(!) chloride remains when the melt is allowed to solidify. For most
transition and posttransition metals the evidence for the formation of " subhalides" is
considerably weaker. The
ion is believed to ellist in
of cadmium in
molte.n cadmium chloride but Can be isolated only through the addition of aluminum
chloride:
Cd + CdCI2
[CdzCI2 )
AJA
___.
Cd 2[AICIJ2
(10.96)
In many cases. although the presence of reduced species is suspected. it is impossible

to isolate them. On solidification the melts disproportionate to solid metal and solid
cadmium(ll) salt.
In solutions of alkali metals in alkali halides. reduction of the cation, at least in the
sense of forming discrete species such as M;. is untenable. It is probable that in the.s e
salts ionization takes place upon solution:
(10.97)
The presence of free electrons thus bears a certain similarity to solutions of these same
metals in liquid ammonia. If the electrons are thought to be trapped in anion vacancies
in the meh , an analogy to F-centers (see Chapter 7) may be made. Undoubtedly the
situation is considerably more complell with the possibility of the electron being
delocaliud in energy levels or bands characteristic of several atoms. but a thorough
discussion of this problem is beyond the scope of this book.23
Complex Formation
Molten salts provide a medium in which the concentration of anionic/ligands can be

much higher than i.s possible in aqueous solutions. The concentration of the chloride
ion in concentrated aqueous hydrochloric acid is about 12M, for example. In contrast,
Corbett. J. D. In Fustd
Sundheim. B. R., Ed.; McGraw-HiU:
New Yodt. 1964; p :141.
378
10 Chemistry In Aqeous and Nonaqueous Solvnts
the concentration of the chloride ion in molten lithium chloride is about 35 M.

Furthermore. there are no other competing ligands (such as H20) present to interfere.
As a result, it is possible to form not only complex ions that are well known in aqueous
solution:
(I U.98)
but also those that cannot exist in aqueous solution because of their susceptibility lo
hydrolysis:
FeCI 2 + 2CICr03
--+
FeCI!-
+ 3ct- -
TiCI3 + 30- --+
(10.99)
(10.100)
(10.101}
Some of these complexes are discussed further in Chapter I I.
Solid Acid and Base

Catalysts
While they are not solvents and solutions in the usual sense of the word, it is convenient here to introduce the concept of solid acids and bases. For example, consider
the class of compounds known as zeolites. These are aluminosilicate structures with
variable amounts of Al(lll). Si(IV), metal cations. and water (see Chapter 16).
Zeolites may behave as Lewis acids at AIJ+ sites. or as Br!3nsted-Lowry acids by
means of absorbed H+ ions. Because they have relatively ope.n structures, a variety of
small molecules may be accommodated within the -0-AI-0-Si- framework.
These molecules may then be catalyzed to react by the acidic centers. Coordinatively.
unsaturated oxide ions can act as basic sites. and in some catalytic reactions both
types of centers are believed to be important. Catalysis by zeolites is discussed further
in Chapter IS.
Solid superacids may be made by treating ordinary solid acid catalysts with strong
or Lewis acids. For example, if freshly precipitated titanium hydroxide or
zirconium hydroxide is treated with sulfuric acid and calcined in air at .500 OC. a very
active solid acid catalyst results. The solids consist mainly of the metal dioxides with
sulfate ions coordinated to the metal ions on the surface. Likewise. a superacid solid
catalyst can be made by treating these metal oxides with antimony pentafluoritle. Both
catalysts contain both
and Lewis acid sites. and they are sufficiently active
to catalyze the isomerization of nbutane at room
Electrode Potentials
a nd Electromotive
Forces
As we have seen. acidity and basicity are intimately connected with electron transfer.
When the electron transfer involves an integral number of electrons it is customary to
refer to the process as a redox reaction. This is not the place for a thorough discussion
of the thermodynamics of electrochemistry; that may be found in any sood textbook
of physical chemistry. Rather. we shall investigate the applications of electromotive
force (emO of interest to the inorganic chemist. Nevertheless, a very brief review of
the conventions and thermodynamics of electrode potentials and half-reactions will be
presented.
Z60fah. G. A.; Prol<a.sh.G. K. S. ;Soouner,J. SutHrocidJ; Wiley: NewYori<.

Tanabe, K.; Misono. M.; Gno. Y.: Hattori, H. NtwSollds. Adds Dlld Bosts; El""vier: Amstcn13m.
1989.
Electrode Potentiols ond Electromotive Force
I. The standard hydrogen electrode (ow
1.00;
f..,
"79
1.00) is arbitrarily
o/0.00 V.
an electrode
2. If we construct a cell composed of a hydr()en electrode and a second electrode

(Mn+ /M) of metal M immersed in a solution of Mn+ of unit activity. we can
measure the potential between the electrodes of the cell. Since the hydrogen
electrode was assigned a potential of 0.00 V, the potential of the electrode,
Mn+ /M, is by definition the same as the measu red potential of the cell. (f the
metal electrode is pcsWvely charged with respect to the hydrogen electrode
(e.g . CuZ+ /Cu), the electrode potentinl of the metal is assigned a positive sign
(Ecu''ICU 2 +0.337 V). If the metal tends to lose electrons more readily than
hydrogen and thus becomes negatively charged (e.g . znZ+ /Zn), the electrode
is assigned a negative sign (Ez..,:n.. "' -0.763 V). This convention is convenient in that it results in a single, invariant quantity for the electrode potential
for each electrode (the z.inc electrode is always electrostatic:aUy negative
whether the reaction under consideration occurs in a galvanic cell or an
electrolytic cell). Most physicnl and inorganic chemists are more interested in
the thermod.vnamics of half-reactions rather than the electrostatic
that obtains in conjunction with the standard hydroge n electrode. The convention related to thermodynamics may be termed the
convention. This convention assigns to the electromotive force (E) a sign such that
t.G,. -nFE
(10.102)
where 6fl is the chare in Gibbs free energy, n is the number of equivalents
reacting, and F is Faraday's constant, 96.485 coulombs equivalent- . It is
necessary to specify the direction in which a reaction is proceeding. Thus if we
consider the reaction
(10.103)
and find that for the reaction, as written, t.G < 0, then (since H+ /Hz is defined
as 0.00 V):
Zn -
E> 0
ZnH +
(10.104)
For the nonspontaneous reaction:
H 2 + Zn2 + t.G
Zn + 2H-
(1o.t05)
> 0, and so for
E<O
(10.106)
Accordingly, the sign of the emf of either a half-reaction ("electrode") or the

overall redox reaction depends upon the direction in which the equation for the
reaction is written (ns is true for any thermodynamic quantity such as enthalpy.
entropy. or free energy). The sign of the reduction electrode is always algebraically the same as that. of the electrostatic potentia1.17
n In the put the dtctroSiaM.: convcnlion has oOcn been ailed the "European COIWCtllion" and the
thermodynamic convcnion pOpUI;uiucl by Latimer 1111, C:itJOIItJif PtJI,trtials <!/ IM fJ1m1 1tiS tJnJ
Tltw Valrtn itr Aqwo11s Saludon; Prcnlke-Hal: En,tcwoocl Clilfs, N1, t9S21 the "Amoricu
cooovcnlion." In an clrort toRCiuccc:cofusion.lbe
"Slod<holmconvcntion" ioo
wtic:ll <ketr<>M pokrtliols tcfcrlo !he dccltostolic pot<niW and nfl{s refer to the tbcnnoclyumic
quanlily. Furt........,.., the rc<:Omi!1Crld:ltion is thai allllldord m/Mction pormli..U be Usle<l ,.
"electrode p<ltentiols" to avoid the possibility or tonflasion
380
10 O.emiotry mAqueous and Nonoqeous Solvents
3. The
equation applies to the potentials of both half-reactions and total
redox reactions:
(10.107)
where Jt'l represents the overall potential with all species at unit activity and Q
represents the reaction quotient.
4. Reactions resulting In a decrease in free energy (fl.G < 0) are
This is a requirement of the second law of thermodynamics. Concomitanlly.
redox reactions in which E > 0 are therefore spontaneous.
S. In aqueous solutions two half-reactions are of special importance: (a) the

reduction of hydrogen in water or hydronium ions:
+ l H2
I M acid H)o + e- --+ H 20
Neutral solution H 10 + e- ---+ OH- + !H2

1M base H 20 + e----+ OH- + lH2
and (b) the oxidation of
ftJ
0.00
-0.414 V
ftJ
(10.108)
(10.109)
-0.828 V (IO.JIO)
in water or hydroxide ions:
+ 2e-
Jt'l
Neutr.tl solution H 20---+ 102 + 2H+ + 2e-
J M base 20H- ---+ 102 + H 20 + 2e-
Jt'l
!02 + 2H ..
I M acid H 20 -
1.229 V
(lO.IlJ)
-0.815 V (IO.JJ2)
-0.401 V
(JO.IIJ)
These reactions limit the thermodynumic srabilitylll of species in aqueous

solution.
6. In calculating the ..skip-step emr for a multivalent species it i.s necessary to
take into account the total change in free energy. Suppose we know the emfs
for the oxidation of Fe to Fe2 and Fe2+ to FeH and wish to calculate the skipstep emf for Fe to Fe, .. :
F e - Fe2 +
FeZ+ -
FeH
Jt'l
E1
0.44
;
-0.77
F e - Fe3 +
Jt'l
fl.G
-
nF = 0. 11/3
ll.G"- - 2 >< 0.44 x F

fl.G
fl.c;0
= 0.037 V
(10.114)
"'
-I x -0.77 x F
(10.115)
-0. 11 F
(10.116)
(10.117)
Although the emfs are not additive, the free energies are, aUowing simple
calculation of the overall emf for the three-electron change.
7. Standard potential or ''Latimer'' diagrams are useful for summarizing a considerable amount of thermodynamic information about the oxidation states of
an element in a convenient way. For example. the following half-reactions may
be taken from Table F. I. Appendix F:
"" As is always I be case when deaJina wilh thennody.,..,.,ic subililies. i1 muSI be borne in mind lhat a
species may possi>Jy be tlwnwdynomicoly unUobt, yet Ainnicoll)' inm.that is. no mechani$m of
low actiWJion eneJXY may exisl for iJs decay.
Electrode Potentiola oncl Electromotive Forces
381
v
+ 1..56 v
+0.90 v
E}J .. + 2.09 v
EfJ = +0.90 v
EfJ = + 1.23 v
EfJ,. +1.70 v
EfJ,. + I.Sl v
(10.118)
MnH + 2e- --+ Mn

Mn3+ + e-
EfJEfJ=
EfJ =
--+ Mn 2
Mn01 + 4H+ + e- --+ Mn 3 + 2H 20

HMno; + 3H .. + 2e- --+ Mn0 2 + 2H1 0
H+ + Mno; + e- --+ HMnO;
Mn0 2
+ 4H +
Mno;
+ 4H+ + Je-
2e- --+ Mn1 + 2H20

--+ Mn0 2 + 2H1 0
Mno; + 8H+ + Se- --+ Mn2+
+ 4H20
- 1.18
(10. 119)
(10.120)
(10.121)
(10.122)
(10.123)
(10.124)
(10.125)
By omittins species such u.s HzO, H+, and OH - , aU of the above information
can be summarized as:

+1.31
1.2:1
1.1 0
The highest oxidation state is listed on the left and the reduction emfs are listed
between each species and the next reduced form, with the lowest oxidation
state appearins on the right.l9
Electrochemistry
in Nonaqueous
Solutions
Althoush the entire d iscussion of electrochemistry thus far has been in terms of
aqueous solutions, the same principles apply equally well to nonaqueous solvents. As
a result of differences in solvation energies, electrode potentials may vary considera bly from those found in aqueous solution . In addition the oxidation and reduction
potentials characteristic of the solvent vary with the chemical behavior of the solvent.
As a result of these two effec ts, it is often possible to cany out reactions in a
n()rul(jueous solvent that would be impossible in water. For example, both sodium and
beryllium are too reactive to be electroplated from aqueous solution, but beryllium
can be electroplated from liquid ammonia and sodium from solutions in pyridine.JO
Unfortunately. the thermodynamic data necessary to construct complete tables of
standard potential values are lacking for most solvents other than water. Jollyla has
compiled such a table for liquid ammonia. The hydrogen electrode is used as the
reference point to establish the scale as in water:
EfJ ..
0.000
(10.126)
"'11>is convenlion orlPnaJcd with lalima and is wiclcsproa4 in Ihe inorpnlc chemical lilctllllrOU of0f1unllldy. Lati.....- used oxidaaion cmfs, and so his cfioatam is a mirTor imaae or lhc one c!raon abe basis or reduction
'Thll has rcsullcd in a wide wrieay or moclfied "l..ati.,....
cliop:>ms, .. dlen with no indicalion or the convenlion employed concemina the sponbncity or die
half-aaaion. To avoid conNsion. arrows (not prescnc in die orilinal Lalimcr diotraml arc recommended. Fun her cliscussion or l..alimor <fill.rams and rdalccleopa may be fOI.IICI in Chaplcr t-4,
"'P:>ny, R. W.; Lyons. E. H.. k . 1ft Tlo' Clwmi11ry o/Ctxmlinllllotr ColfiiHHIIJds; Baitar, J.
Ed.; Van
New YOI1c. tm; pp 669-67 t.
" Joly, W. L J. Clwm. t:Ju.:. 1956. JJ, 512-517.
c.. Jr..
382
10 Che mittry ;,. Aqueo a ncl Nonaqueous Solve11ts
A single example of the application of electrode potentials to chemistry in ammonia will suffice. The Latimer diagrnm for mercury in acidic solution is
Hg2+
Hg[
Hg
nto7
and for the insoluble mercury(l) iodide the diagram is

Hg1 +
Hg
Hg2 12
lt may readily be seen that the mercurous ion (whether free or in Hg2 12) is thermodynamically unstable with respect to disproportiornuion in ammonia, in contrast to
its stability in water.
Electrochemistry in nonaqueous solvents is not merely a laboratory curiosity. We
have already seen batteries made with solid electrolytes (sodium beta alumina, see
Chapter 7) that are certainly "nonaqueous." In looking for high-efficiency cells one
desires the cathode and anode to be highly reactive (large positive emf) and to have a
low equivalent weight. In these terms. lithium appears to be highly desirable. Its very
reactivity, however, precludes its use in aqueous systems or even liquid ammonia.
One successful battery utilizing lithium has been developed using sulfur dioxide or
thionyl chloride (OSCiz) as solvent and oxidant. Others involve weight-efficient
lithium metal with other oxidants and solvents.ll Highly efficient batteries of this sort
are widely used in specialized applications where light weight and long life arc
important.
Hydro met allurgy
TraditionaRy the wmmns of metals from their ores has been achieved by
pyrometallurgy: the reduction of relatively concentrated metallic orcs at high temperatures. The reactions of the blast furnace form a typical clUllllple (see also page
3n):
Fe2 0 3 + 3CO
-----+
2Fe + 3C01
(10.127)
C02 + C
-----+
2CO
(10.128)
Carbon monoxide for the reduct ion of the iron is formed not only from the recycling of
carbon dioxide (Eq. 10. 128) but also from the direct oxidation of the coke in the charge
by hot air:
2C+01
2CO
(10.129)
The energy released by the combustion is sufficient to raise the temperature well
above the melting point of iron, IS3S c. One of the incentives for development of
alternative methods of producing metals is the hope of finding less energy-intensive
processes.
Hydrometallurgy is not new; it has been used for almost a century in the separation of gold from
ores. This process is typical of the methods used. Gold is
normally a very unreactive metal:
- 1.69V
Jones. K. J.; tblch. E. S. Jr. /ltd. Rn. Drv. feb. 1981. U , t82; Mar. 1'81. H . 89.
(10.1JG)
Problems
383
With such a
oxidation e mf, it is too noble to react with either 0 2 (E."'
+ 1. 185 V) or CJ2 (E' 2 + 1.36 V). By complexation of the Au(l) ion. however, the
emf can be shifted until it is much more favorable:
Au
+ 2CN- -
Au(CN)i
+ e-
E'"' +0.60 v
(10.131)
Oxygen in the air is now a sufficiently strong (and cheap!) oxidizing agent to effect the
solution of the gold . It may the.n be reduced and precipitated by an active metal such
as zinc powder CE' = - 0.763 V). Such hydrometallurgical processes offer definite
advantages:
I. Low-grade ores may be leached, with complexing agents if necessary, and

profitably exploited.
2. Complex ores may be successfully treated and multiple metals separated under
more carefully controlled processes.
3. Since the reactions are carried out at room temperature, energy savings are
possible.
4.
no stack gases are involved, air pollution does not present the problem faced by pyrometallurgy.
These aspects do not fonn an unmixed blessing, however. If the metal must be reduced by electrolysis, the process may become energy intensive. Thus auractive
solutions to this proble m are reduction of more valuable gold by le.s s expensive zinc
and of more valuable copper by scrap iron. Finally. in view of the large amounts of
waste water formed as byproduct, one may be trading an air pollution problem fur a
water pollution problem . A compurison of the two types of processes is given in Table
10.6.
Related hydrometallurgic methods may allow the use of bacteria to release copper
from low-grade ores, or the use of algae to concentrate precious metals such as gold
(see Chapter 19).H
,, Brierley, C. L. Sd. Amu. t912. 247(2). 44-53. DamaU, D. W.; Greene, 8 .: Henzl. M. T.: Hosea.J.
M.; McPherson, R. A.; Sneddon. J.; Alexander, M. D. Environ. Sci. Trchnol. 1986. 20. 206-208.
Table 10.6
Pyrometollurgy
A comparison of
pyronoetollurgy cmd
hydrometolurgr
Enei'!Y
consumption
Dust
Toxic sases
Solid residues
Treat.ment of
sulfide ores
Treatment of
complex ores
Treatment of
low-grade ores
Economics
Because hish temperatures

(about ISOO"C) are involved,
reaction rates are hish but
much enei'!Y is consumed.
Heat recovery systems are
needed to make the process
economical. Heat can be recovered readily from hot
gases (although the equiprnent needed is bulky and
expensive), but is rarely re
covered from molten slag or
metal, so thai a srear deal of
energy is lost
Most processes emit large
amounts of dust, which must
be recovered to abate poilulion or because the dust itseU
contains valuable metals:
equipment for dust recovery
is bulky and expensive.
Many processes generate toxic
sases. so that reactors must
be gas-tight and the gases removed by scrubbers or other
systems: this is expensive, especially when the gases are
hot and corrosive.
Many residues. such as slags,
are coarse and harmless, so
that they can be stored in exposed piles without danger of
dissolution, although the piles
may be esthetically
unaccepcable.
Sulfur dioxide is generated,
which in high concentrations
must be converted to sulfuric
acid (for which a market must
be found) and in low concentrations must be disposed in
other ways (avUable but
expensive).
Unsuitable because separation
is difficult.
Unsuitable because large
amounts of energy are required to melt gangue
materials.
Best suited for
operations requiring a large capital
investment.
Bec:ause low temperaiUteS are

involved in dissolution prothey require little
energy, although reaccion
rates are slow. However, a
requirement for
ning or for deaning eftluents
and recovering reagents may
more than offset this energy
No problem, because materials

handled usually are wet.
Many processes do not generate

gases, and if they do, reactors
can be made gas-tight
Most residues are finely divided

solids that, when dry. create
dust problems and, when wet,
gradually release metal ions
in solution that may colllaminate the environment .
Ores can be treated without
generating sulfur dioxide,
eliminating the need to make
and market sulfuric acid:
sulfide sulfur can be re
covered in elemental form.
Suitable.
Suitable if a selective leactung
agent can be used.
Can be used for small-scale operations requiring a low

capitnl .investrnent.
From Habashi. F. Chmr. Enlf. Nnn. 1912. 60(61. 46. tJK<I with permission.
384
Probletns
Problems
385
10.1 Suggest the specilic chemical and physicAl ifucraetiom responsible for the revenal or
Eqs. 10.3 and 10.<4 in water unci ammonia solutions.

10.2. Usi1111 u Born-Haber- cycle employina the vorious enetlies conlributin.sto the formation of
M. e(NH 1); species in ammonia solutions. explain why such solutions form only with
the most active metals.
10.3 When I mole of N10, is dissolved in sulfuric acid. 3 equivalents of base are produced.
Conductivity s tudies indicate that " 6 for N:t<),. Propose an eQUDJion representing the
sdvdysis of N:t<), by sulfuric acid.
10.4 What is the strongeSJ ucid listed in Fig. 10.1? The monsest base?
10.5 From Fig. 10.1 detennine bow the foUowi1111 solutes wiU react with the solvenas. and how
the equilibria will lie, thai is, wiD the sdute be completely leveled or in equilibrium? Sune
whether the solution formed in each case wal be more acidic or more basic thun the pUre
sdvent.
Solute
Solvent
Acetic acid
Water
Ammonia
CH1C(OICH1
CH1 C(O)CH1
PhN H PhNHPbNHPhNW
Ammonia
Water
Ammonia
Water
Acetic Acid
Sulfuric acid
10.6 Construct the Latimer W.,ram for 1111,.ancse in bo:iic solUtion Cfrom value5 in T3ble F. I),
and predia which oxidation states wi be Slllble. E.xplain 1he.:source ofinst:>bility for each
unsmble .species.
10.7 CaJculme the pOtential for the oxidation of UQ, tO
in acid solution from the
fdlowin.s informotion.
uo;
uoi
+ e- - - UO,
+ e- - -
uo;
"-
0.66 V
o. t6
10.8 Usc the utimer diugmm for plutonium in ucid I<Oiutiun below to unswer 1hc fdlowing
questions.
-1.00
t .O)
- t.lJ
a. Would you expect plutonium rnetolto react wi1h water'?

b.
Pu is SUlble in concentrated acid but disproportionate$ to

acidities. Explain.
c. PuO; tends 10 dispr0p0nionale to Pu and

this reaction be least likdy to occur?
PuQi and
w at low
PuQi. Under what pH con"di1ions would
10.9 Wtlh cquacjons and words describe what hllppens
a. when metallic pOtassium is dissolved in ammonia to ronn a dilute solution.

"- when more pOtassium is added to fonn COfiCefllr.lted solutions.
386
10 C h emi11ry In Aque ous ond Nonaq ueous Solvenes
c:. when solutions (a) or (b) are evap01111ed Cllrdully in

d. when (a) is tre:llt:d wilh
How can (d) be considered a tevelina reac:ion?
10.10 Consider eac:h of the foDowing solvents individually: ( I ) ammonia. (2) acetic: acid, (3)
sulfuric acid.
a. Give equa1ions tor autoionizaeion of ehe pure solvent.

b. Discuss whae will happen if CH,COOH is dissolved in each of lhe solvents. that is.
what ions wiU form. Give appropriate equorions. Will the solution be acidic or basic
wieh respect to the pure solvem? Will the solute act as a weak or a strong acid (base) ?
e. Give an example of a strong base, a serona acid. and a
reaction.
IG.Il As a working hypothesis. assume thw you uccept ehe solvene system piceure or OPO, and
a valueofS >< to- mol1 L- z for the ion produce. See upapCI SC4Ie l'orOPCI,. draw the
equivalene ofF'" . 10. 1 l'or it, and discuss how you would ao about obtaini,. data for
compounds 10 compleee your diagram.
biliey conseane, K ..._A
.
fi-'
(AulCNl; J
I0. 12 .,.._
I .... sta
'"' U(CN1:! IS de ..... o.s [AunCN- r
a. F rom ehe
f!> of +0.60 V for Eq.
10. 131 estimate K .
b. Qualimtively descnbe why this compte,. is so stable.

t0.13 Corrdoue the behavior of various soluees in " supcrocids" with their gaspha$e pruon
affinities. What faaors besides proeon affinities ulrect their solution chemisery? Prcdia
wh:u species will be presenl when XH 1 (Group VA, IS). H, X (Group VIA. 16) and HX
(Group VIlA, 17) are dissolved in " superocids ...,.
10.14 Single-crystal " ccslum electride" is nlmost entirely diomaanetic. Rcal01Cilc this with the
fonnulation ICsOigancllr e-. Is there o porodox here?
10. 15 On page ln. HgO, is meneioned as an exception to lhe obviously intuitive rule ehaa
vrrsu." C..n you
a reason
" good acceptors should not be good donors. nd
why Hg(lll mi&hl be parndoxical?
10. 16 Sugges1 equilibria for ehe redox c:hemisery 01 an llluminum electr ode and show how 1he
IX>'enlial can be related to the [0- 1(puge .)74).
37ft it was staled thai one of the tlifficulties with the cell <.lescribed there
10.17 On
d iffusion of Ct.Ct,. Explain .
10.18 Is the d iffusion discussed on P."'CC .)76 ond in Problem IO. t7 :>. flltul
you know from
chemistry about a simple
cell: Zn 1
was
CH im: Recall what
z.rr I eu!l Cu.)
}4
Obh. G. A.; Shen. J. J . Am.
Soc. 11173. 9$, l.5112-JS84.
Chap
er
11
Coordination Chemistry:
Bonding, Spectra,
and Magnetism
C oordination compounds have been a challenge to the inorganic chemist since they
were identified in the nineteenth century. ln the early days they seemed unusual
because they appeared to defy the usual rules of valence (hence the label ' 'complex"
compounds). Today they comprise a large body of current inorganic research. Althoush the u'-ual bondina theories can be extended to accommodate these compounds,
they still present stimulatins theoretical problems and in the laboratory they continue
to provide synthetic challenaes. One class of coordination compounds, those involving metal-carbon bonds, is the focus of an entire subdiscipline known as
organometallic chemistry (Chapter 15), and the field of bioinorganic chemistry (Chapter 19) is centered on coordination compounds present in living systems.
The modem study or coordination compounds began with two men, Alfred
Werner and Sophus Mads Jlilrgensen. Both were astute chemists. not only in laboratory aspects but also in the areas of inte.,retation and theory. As it turned out. they
differed fundamentally in their intC'l>retation of the phenomena they observed and
thus served as protagonists. each spurring the other to perform further experiments to
augment the evidence for his point of view. From our vantage point nearly a century
later. we can conclude that Werner was " right" and Jlilrgensen was "wrons" in the
interpretation of the experimental evidence they had. Indeed. Werner was the first
inorganic chemist to be awarded .the Nobel Prize in chemistry (1913). 1 Nevertheless,
Jtsrgensen's contributions should not be slighted- as an experimentalist he was sec-
1 Mer Alfre<l
won 1he prize. it long appeared that he miehl be the only inorpnic chemist to
receive it. Then sixty ycurs IDler in 1973. Geoffrey Wilki'*'n and E. 0. F'asc:her share<! the Nobel
Prize in chemistry for 1heir worlt on ferrocene (see Chapter IS). (For a pcrsonolliC.COUIIt from tile
Chm. 1975, /00, 273-278.)
Alnericnn side or the Atlon1ic, see Wilkinson. C . J .
However. in the past couple or decades. u number or prizes have been awarded for inorpnic
chemistry or closely rdalcd work: W'olbm Lipscomb (19671 aad H. C. e......, (19791 for their
lheore!ial and synrheric work in boo'UIC dlemislry (sec ChaptQ' 16); Roald Holfii\IM (1981) foc hi
theor<fical work in orpnomctallic dlcmistry (see CNpier 151: an:t Herory Taube (Ill&)) for his
r=ordl in inorpnic kin<IICS (sec Cbaplcr
m.
387
388
11 CGdination Chemi<try: Bonding, Spectra, and Magnetism
ond to none. and had he not been prejudiced by some of the theories of valence
current in his day. he might well have achieved the same results and fame as Werner.2
Werner. in formulating his ideas about the structure of coordination compounds,
had before him facts such as the following. Four complexes of cobalt( Ill) chloride.with
ammonia had been discovered and named according to their colors:
Complex
CoCI3 6NH 3
CoCI3 SNH 3
CoCI1 4NH 3
CoCI3 4NH1
Early name
Yellow
Purple
Green
Violet
LUleo complex
Purpureo complex
Prnseo complex
Vio/eo c.omplex
One of the more interesting facts about this series is that two compounds have
identical empirical formulas. CoC13 4NH 3 but distinct properties. the most noticeable
being a difference in color. Furthermore, Werner noted that the reactivities of the
chloride ions in these four compounds differed considerably. Addition of silver nitrate
resulted in different amounts of precipitated silver chloride:
CoCI 3 6NH 3 +excess Ag -
3Ag0(s)
(IJ.l)
Co03 SNH1 +excess Ag +
2AgO(s)
(11.2)
Co03 4NH3 +excess Ag+ -
IAgO(s)
(11.3)
Reaction 11 .3 occurs for both the praseo and vio/eo complexes.

The correlation between the number of ammonia molecules present and the
number of equivalents of silver chloride precipitated led Werner to the following
conclusion:l
"We can thus make the general statement: Compounds M(NHJsX3 [M = Cr. Co:
X ; Cl. Br. etc.) are derived from compounds M(NH3),.X3 by loss of one ammonia
molecule.
With this loss of an ammonia molecule. however, a simultaneous change in
function of one acid residue X ( chloride ion) occurs ... (In) CO(NH 3 ),CI3
two chlorine atoms behave as ions and are precipitated by silver nitrate at room
temperature. while the third behaves completely analogously to chlorine in chloroethane. that is. it no longer
as an ion."'
From this conclusion Werner postulated perhaps the most impertant part of his
theory: that in this series of compounds cobalt exhibits a constant coordination
number of 6. and as ammonia molecules are removed. they are replaced by chloride
ions which then act as though they are covalently bound to the cobalt rather than as
free chloride ions. To describe the complex chemistry of cobalt. one must therefore
consider not only the oxidation state of the metal but also its coordination number.
l For c!iscus!ion of the ear1icSI WOt1< in coordinlllion chemislry, see Koutrman, G. 9 . J. Chrm. due.
1959. J6. 521-S27: KaufTmnn. G. B. Ciaslcs ito Conrdinutlmt Chrmlsrry; Dover: New YO<i<. 1968
(Purl I : Tu
PU{H'n uf A./fr<J W<rnrrl; 1976 (Pari 2: Srlit'd p_., 17911-18991: 1978
(Purl J: Twmlit'lh-C<"nlltry Puptrs. 1904- 1915).
>Werner.
Ch<"m. mJ.J. 267-342. Forutransbtionscerhesecondreferoncein F001no1e
2. All bracketed material and ellipses ore ours.
Coor d ination Chemiatry: l anding, Spectra, and Mognelisnt
Werner thus formulated these fou r salts as (Co<NH 3),.)CI,,
389
a nd
Realizjng that these formula tion s implied a precise statement of the numbc!r of
ions fo rmed in solution. We rner chose as one of his first expe rimental studies measurement of the conductivities o r a lurge number of coord ination compounds.' Some
or the results or this work are lis ted in Table 11. 1 toaether with values for simple ionic
compounds for comparison .
Table 11.1
Conclo.ctivities of
c:oordinnrian co-nels
Empirical
fonnulo
PtCI 4 2NH,
PtCI4 2NH,
3.52b
(trans)
(cis)
1 : 1 Bectrolytes
NaQ
PtC143NH,
PtCI.-NH3 KCI
123.7
96.8
106.8
1 : 2 aiMI 2 : 1 Electrolrtn
CaOz
CoO,SN H,
CoBr35NH,
CrC1,5NH,
CrBr3SNH,
PtCI4 4NH,
PtCI.-2KO
260.8
261 .3
2S7.6
[Co(NH31,CIICI:
260.2
280. 1
228.9
2S6.8
1 : 3 a..d 3 : 1 Bectrolytn
LaCI,
CoCI,-6NH,
CoBr,-6NH,
CrCI,6NH,
PtCI.-SNH,
393.5
431 .6
426.9
441.7
404
[CO(NH 3)JCI,
[COINH 31,JBr3
(CrtNH3)0)CI,
(PttNH3 J,CI)0 3
1 4 Be<trolytes
This ;. the molar conductivily mcaoured ut u concent..Cion of
0.001 M. Values are from Werner Afl\l Miol&ti,
for
(Pt(NH:m<:J.JO,. which is from Vladimirov, N.; Clluaacv, L.A.

Compt. Rntd. 1915. /61J, 840.
The theoretical value is. of course, zero, bul iqlurities or u
reaction with the solvent waiCI' could produce u small
concenlntion of ions.
I
WCI'nCI''s terminoqy :lnd symbotiom diiTorcd in sm:tn, rclatlve.ly
WDys from Ihal u...S
loday. For exaJ111)1e. WCI'1ICI' referred to oxidotion siUie as "primaty valence"
and
coordinalkln n&llllber :IS
valcnc.c" (Nrl>rllolrllll. Abo. he wrocc fomwlas as
(Co':;''')O,. ins'-! of ICoiNH31,0101
'WCI'1ICI'. A..; Miolali. A. Z. Plrp. Chffll. Cu {pti/tl lltl. 11. lS-SS. lbiJ. 11M. 14. SOI>-S21.
390
11 Coordination Chemistry: 8Gflding, Spectra, and
A Sond important contribution thai Werner made to the s1udy of coordination

chemistry was the postulate that the bonds to the ligands were fixed in space and
therefore could be treated by application of structural principles. By means of the
numbers and properties of the isomers obtained. Werner was able to assign the correct
geometric structures to many coordination compounds long before any direct experimental method was available for structure determination. Werner's method was that
used previously by organic chemists to elucidate the structures of subslituted benzenes. namely isomer counlin&. Werner postulated that the six ligands in a complex
such as
were situated in some symmetrical fashion with each NH,
group equidistant from the central cobalt atom . Three such arrangements come to
mind: a plan or hexagon-similar to the benzene ring-and two polyhedra. the lrigonal
prism and the octahedron. The trigonal prism is closely related lo the octahedron,
being formed by a 60" rotation of one of the trigonal faces of lhe octahedron (in fact,
the octahedron can be considered a trigonal antiprism). For a " disubstituted" complex, MA4 B2, the planar arrangement gives three isomers. the familiar ortho, meta.
and para arrangements of organic chemistry. The trigonal prism yields three isomers
also. but lhere are only two octahedral arrangemen1s for this formulation. The tolal
number of isomers expec1ed for each geometrical arrangement together with the
experimental results for various compositions are listed in Table 11 .2.
In every case Werner investigated, the number of isomers found was equa110 that
expected for an cxtahedral complex. For [CO(NH,)4CI 2]CI. for example. two isomers
perfect.
(one violet and one green) were observed. Although the correlation here
it must be borne in mind that the observa1ion of two instead of three
for this
compound and others constitutes negative evidence concerning the structure of lhese
complexes. Even. though Werner worked carefully and examined many systems. there
was always the possibility. admiuedly small. that the third isomer had escaped his
detection. The failure to synthesize a compound. to observe a particular property. or
to effect a particular reaction can never be posi1ive proof of the nonexistence of thnt
compound. property, or reaction. It may simply reflect some failure in technique on
the part of the chemist. One well-known example of the fallacy of negative evidence
involves the overthrow of the dogma1ic belief in the chemical inertness of the noble
gases (see Chapter 17).
Werner was correct. however. in his conclusions concerning the octahedral
geometry of coordinmion number 6 for cobali(IIJ) nnd platinum(IV). He was also
correct, and on a firmer logical footing, in his assignment of square planar geometries
Table112
Nvmb.n of isomen
npected a..cl found fer
C.N. = 6
'MA$8
MA,B,
Planar
..Triganal prismatic
""f'l "'.,... -:: I ...3'
3
3 -
Odahedrvl
I
2
2
I
2
2
Valence Bond Theory
391
to the four-coordinate complexes of palladium and platinum from the fact that two
isomers had been isolated for compounds of formula MA,B . The most likely allernalive structure. the tetrahedron, would produce only
iSomer for this composition.f> The ability of Werner and others to
the correct structures from indirect
data and logic was hailed by Henry Eyring:'
"The ingenuity and effective logic that enabled chemists to determine complex
molecular structures from the number of isomers, the reactivity of the molecule and of
its fragments. the freezing point. the empirical formula, the mole.cular weight, etc., is
one of the outstanding triumphs of the human mind."
Bonding in
Coordination
Compounds
Valence Bond
Theory&
There has been much work done in attempting to formulate theories to describe the
bonding in coordination compounds and to rationalize and predict !.heir properties.
The first success along these lines was the valence lxJnd (VB) theory applied by Linus
Pauling and others in the 1930s and fOllowing years. In the 1950s and 1960s the cryswl
field (CF} theory and its modifications, generally known under the label ligand field
(LF) theory, gained preeminence and in turn gradually gave way to the molecular
orbiwl (MO) theory. Although both the valence bond and crystal field theories have
been largely displaced as working models for the practicing inorganic chemist, they
continue to contribute to current discussions of coordination compounds. Because
they shaped the thinking about these compounds in the very recent past, the earlier
models still serve as the backsround against which newer ones are evaluated. Moreover. certain of their features remain part of the conceptual framework and vocabulary used by current chemists. Hence they must be appreciated in order to have a full
understanding of modern constructs.
From the valence bond point of view, formation of n complex involves react ion
between lewis
(ligands) and a lewis acid (metal or metal ion) with the formation of coordinate covalent (or dativel bonds between them . The model utilizes
of melal s. p. and d valence orbitals to account for the observed
struclures and magnetic properties of complexes. For example. complexes of Pd(li)
and Pt(ll) are usually four-coordinate. square planar. and diamagnetic. and this
arrangement is often found for NiUI) complexes as well. Inasmuch as the free ion in
the sround state in each case is paramagnetic (dK. J F). the bonding picture has to
first crysraliq:r.lphic confirmation of Werner' s assinmCOt of octallcdral eeomctry to Pill VI

complees was not published until t92t. some twenty yean aOu his theories were
(Wyckoff. R . W. G .; POSI\iak. E.J. Am. Chem. Soc. 1921.43, 2292-2309; !NH.b!PtO..JJ. The >quate
plan"' structure of 1'11111 complccs was cooftrmed the net year (Dickinson. R. G. J . Am.
Sm. 19Zl. 44. 2404-2411; K,!Pt04 1). ln1Cr0$ti'1!1y. neither popc:r mentions Werner and in fact. the
second one stat"": " It would probably be anticpoted rh.>t in the chloroplatinotcs. fClCJrchl<lrine atoms
would be t:fOUpc<l about each platinum arom; 001 the form und dimens;o..s of this tvoup us well us its
situation in the structure could sc:arcety be predicted wilh Sllfety...
, Eyrintl. H . Chm. En11. Nrws 1963.41111. S.

The classical accounl or valence bond theory as applied to COO<dination canpalllds is probably
Paulifll's book. TM Nu111,. of tlr Clwmicol Bond, lrd ro.; Cclmell Univ.:rsity: Ithaca. NY, 1960.
For a more recent discussion pc<Jaining to coordination compounds and Ofilnomerallic compouncb.
see Minaos. 0 . M. P.; Zhcnyang. L. StrUCt. BonJin11 CBnlhtl 19911. 72. 73-tll.
392
11 c......dination Chemistry: Bonding, Spectra, nnd Magnetism
include pairing of electrons as well as ligand-mellll-ligand bond angles of90". Pauling

suggested this occurs via hybridization of one (11 - I)d, the n.t. and two np orbitals to
form four equivalent dsp2 hybrids directed toward the corners of a square. These
orbitals then participate in covalent a bonds with the liaands. the bondins electron
pairs being furnished by the ligand s. The eight electrons that were distributed among
the five d orbitals in the free ion are assigned as pairs to the four unhybridiz.ed metal d
orbillll.s (Fig. ll.la).
With some ligands, such as o -, Ni(ll) forms four-coordinate complexes that are
parnmagnetic and tetrahedral. For these cases, VB theory assumes the d orbital
occupation of the complex to be the same as that of the free ion, which eliminates the
possibility that vale nce-level d orbitals can accept electron pairs from the ligands.
Hybrid orbitals of either the spJ or sdJ type (the Iauer involving n-level d orbitals) or a
combination of the two provide the proper symmetry for the u bonds as well as
(a)
li Jl
*lilli
6p
61
li li
Jtp! hybri<l emil...
lii-
El<raftJJ fnwnQ"IiJ"""
s.,.- pl>lllll - r y
sp' hyMol '""'"'

Ell"CU'Om
0 . lij:w!UN
T<H".>l._v..,l gJm:lry
4p
l<l
li li li
u
j_ j_IJi li li li Jllil- __
S(JJd: hybrid OlbiiiiiJ
ElectR>M llml F" 11&..-..k

Ocl;>hcdnl 'oomc:lry
Jl
Jl *'li li.,J Jl Ji ll Jll

J7
h)'ll<id orbilols
Elc<tn>M flml I'IHJ lipids
Oclol>odnl - r y
Fig. 11.1 Orbital

depic:tina the valence bond clescripeion of the metal-lipnd bonds
in (al (PtCI.f". (b) [NiCI.f". (c) [CoF.JJ-. and (d) ICO(N H,),.JJ.
Valence Band Theory
393
allowing for the magnetic properties (F.g. ll.lb). The examples presented here illustrale a use.ftJI rule. originally called " the magnetic criterion of bond type." which
allows prediction of the seometry of a four-<:oordinate dH complex if its magnetic
propertie.s are known : diamagnetic square plannr; paramaanetic = tetrahedrnl.9
The valence bond picture for sixcoordinate octahedral complexes involves d 2sp 3
hybridization of the metal (Fig. ll . lc. d). The specific d orbitals that meet the symmetry requirements for the metal- ligand u bonds are the d_, and d..,:_., (page 396). As
with the four-coordinate d 8 complexes discussed above: the presence or unpaired
electrons in some octahedral compounds renders the valence level (n - l)c/ orbi1als
unavailable for bonding.
is true. for instance, for paramagnetic (CoF,f- (Flg.
l l . lc). In these cases , the VB model invokes participation of n-level d orbitals in the
hybridization.
The Electroneutrality
Principle and Back
Banding
One difficulty with the VB assumption of electron donation from ligands to metal ions
is the buildup of formal negative charge on the metal. Since this is a problem thai.
arises. in one form or another. in all complete treatments of coordination compounds,
the followins discussion is appropriate to all current bondina models.
Consider a complex of Co(ll) such as (CoLt.f+. T he six ligands share twelve
electrons with the metal atom, the reby contributing to the formal charge on the metal a
total of- 6, which is only partial ly canceled by the metal's ionic charge of + 2. From a
formal c.harge point of view, the cobalt acquires a net - 4 charge. However, Pauling
pointed out why metals would not in fact exisl with such unfavorable negative
charges. Because donor atoms on ligands are in generul highly electronegative (e.g.,
N. 0 . and the haloaensl. the bond ins electrons will not be shared eq ually between the
metal and ligands. Paulins sugges1ed that complexes would be
stable when the
electronegativity or the ligand was such that the metal ac hieved a condition or
essentially ze.r o net ele<:trical c harge. This tendency for zero or low electrical chafBt:s
on atoms is a rule-of-thumb known as the elrcrmnc-ufrliry prindplt, and it is used 10
make predictions regarding electronic structure in many types of compounds. not only
complexes. Pauling has made semiquantitative calc ulations correlating the stability of
complexes wi1h the charges on the central me1ul atom .lo Some typical results are:
IAUNH 3),] 3+
Be= -0.011
40 = -0.24
8H = 2.32
Total = + 2.00
Be .. -1. 12.
60 .. - 0.36
12H =3.48
Total +2.00
AI -0. 12
60 .. - 0.36
3.48
12H
Totul
+3.00
Al
- 1.08
6N ..
1.20
ISH= 2.88
Total= + 3.00
Although the above values involve very rough aPProximations. they do indicate
qualiratiely how buildup of excessive nesative charge on a metal can des1abil ize a
complex. Within the sroup of complexes shown. JBe(H2014 )1+ and
are 1
stnble, but the other two are not. Four water molecules effectively neutralize the + 2
ionic charse or beryllium, but six water molecules donate 100 much electron density.
'An exccplion lo Ibis rule i. the panunaanetic complex, IR:PIOII"R' h Ni (R - BJ: R' 1'11. in
which the ccnrrol Ni(ll) is botlnd to two oxYCen lllld1wo nilrocen oms in a planar .,.,.,.,.,,. Sec
Frilcnmcl. T. ; Pcten. W.; Wundedictl. H.; Kuchcn, W. A"A't'W Chtm. Int. Etl. Enl(l. 1991. J l.
6t2-{,IJ.
to
Po1.t1inc. L. nw Ntz!Mrt qf tM
pp 11'2-174.
CAtmkul Bt>NI. lnt
w.; Cornell
University: Ithaca. NY. t960:
394
11 Coc><dinotian Chemistry: Bonding, Spectra, and Magnetism
( a)
I b)
er-e
Fig. 11.2 Effect of metal-ligand ,.. bonding: !he

bond
is increased and I he
C-0 bond
is ckcreased. (a) VB vicwpoinl: ..-bond bel ween J orbilal on Cr utorn and
p
on.C
(b) MO viJewpOint : ..-bond between d Ofbital on 0" ulom and
unlibonding orbilal (n) on the CO ligand.
In contrast, Atl+ can adequately accommodate six water molecules: however. the
nitrogen donor of 1he ammonia ligands is not sufficiently electronegative to prevent
the buildup of excess electron density on aluminum in [AI!NH,}h]H, with the result
1hat the complex is unstable.
In apparent contradiction to the electroneutrnlity principle. the re are many complexes in which the metlll exists in a low oxidation state and yet is bonded to an
element of fairly low electronegativity. Among the most prominent example.s are the
transition metal carbonyls. a large class of compounds in which the ltgand (CO) is
bound to the central metal through carbon. The source of stability in these complexes
is the capacity of the carbon monoxide ligand to accept a 'back donation of elect ron
density from the metal atom. Within valence bond theory. this
can be
described in terms of resonance:
Cr-ClEiO: ... Cr=C=Q

(I}
(ll)
To whatever extent canonical form II contributes 10 the resonance hybrid. electron

density will be shifted from chromium to oxygen. A more precise el!amination of this
indicates 1hat the dclocalization of the electron density occurs via ..-overlap or
a J orbital on the metal with an orbital of appropria1e symml!lry on the carbonyl
ligand. In valence bond theory, the ligand orbital would be one of the p orbitals of the
atom (thus making it unavailable for a " bond to the oxygen). whereas the
molecular orbttal theory would speak in terms of overlap with 1he ..- antibonding
orbital of
monoxide (Fig. 11.2). In either representation a 1r bond forms
between metal and ligand and provides a mechanism for a shift in electron density
away from the metal toward the ligand. The formation of"' bonus of this type will be
discussed at greater length later in this chapter.
Crystal Field
Theory
The modellhat largely replaced valence bond theory for interpreting the chemistry of
coordination compounds was the crystal field theory, first proposed in 1929 by Hans
Bethe. ll As originally conceived. it was a model based on a purely electrostatic
II
Belhe, H. Ann. Phys. 1929. J . I}S.206.
Crystal Field Theory
395
me
interaction between the lisands and

metal ion. Subsequent modifications, which
began as early as 1935 with papers by J. H. Van Vleck,tZ allow some covalency in the
interaction . These adjusted versions or the oriainaltheory generally are called ligand
field theory.t3 It is an interesting feature of scientific history that, although the
development of cryslal and ligand field lheories was contemporary with tha t of
valence bond theory. they remained largely within the province of solid state physics
for nbout20 years. Only in the 19S0s did chemists begin to apply crystal field theory to
transition metal complexes. t4
Pure crystal field theory assumes lhat the only inleraction between the metal ion
and the ligands is an electrostatic or ionic one with the ligands being regarded as
point charges. Despite this rather unrealistic premise, the theory is quite
succ.essful in interpreting many imporlant properties of complexes . Moreover. the
symmetry considerations involved in the cryslnl field approach are idenlical to those
of the molecular orbital method. The electrostatic model thus serves as a gOOd
introduction to modem theories of coordination chemistry.
In order to undersland clearly the interactions that are responsible for crystal or
ligand field effects in transition metal complexes, it is necessary to have a firm grasp of
the geometrical relationships of
d orbitals. There is no unique way of representing
the lived orbitals, but the most convenient representations are shown in Figs. 11 .3 and
11.4. In fact, there are six wave functions that can be wriuen for orbitals having the
typical four-lobed form <d.., and dr- Y: for example). lnumuch as there can be only
live d orbitals having any physical realily, one of lhem (the d.>) is conventionally
regarded as a linenr combination of two others. the cl:>-,; and
Thus these latter
IWO orbitals have no independent exlslence. but the
can be thought of u having the
average propenies of the two ( Fi&. 11 .5). Therefore-. since both have high electron
density along Jhe axis, the d; orbital has a large fraction or its electron density
concentrated along the same axis. Also. since one of the component wave functions
(d:=-x'l has lobes a long the x axis and the o ther (d:-,;1 along the y axis. the resultant
d.: orbital has a torus of eleclron densily in the xy p lane. This xy component. which is
often referred to as a "doughnut" or a "collar: is frequenlly neglected in pictorial
represenlalions, es pecially when an attempt is beina made to portray a ll lived orbitals
sinhlltaneously. Nevenheless, it is important to remember this xy segment of che d:?
orbital .
The live cJ orbitals in an isolaced, gaseous meml ion are degenerate. Ifa spherically
symme.tric field of negative charges is placed uround the mecal. the orbitals will remain
degenerate, but a ll of I hem will be raised in energy ns a result oft he repulsion between
me
u_..
d:::r.
o: Van Vleck . J. H . J.
Plrys. 1935. J. IIOJ-1!06.
Then: is some inc:onsi5tency in che u"" ol ohe Wbct ua>nd fteld lheory'"
nnd other
sources. In some instances it is taken :lS e.scntially a sulntilule for lhc label crystal field theory on
tile premise chat llle loiter is mi<lcadina (see. for example. ScllUifcr, H. L : Cilicmam. G. Bruir
Principl.-s ofLiKGifJ Fitld n....,.,: Wiley-lnoCI'M:iencc: New Yorlt. t%9: p 111. AI the othcrcxlremc
are those who U.'IC clle term to
a molecular orl>illJI de:ocriptioo. bonclinr: in complexes. II ;.
si/'ifoc:ont chat Van Vkck in his 111)3 l"'llC' wus see kina co reconcile lkthe s clocory with Mullikcn"s
molcculor ortilal ai)(><Oadl. TIU clfon b.:os been des<:ribed by &llh:wscn I> Foulnote 141 as
""incotpot:!lina the best fc.otura ol belch the pure c:ryslllllickllheory ullll molecular orl>itoltheory.
U seems appropriacc. then. 10 ,jew tiaond field theOty as o modd lhlll owes illi orilins lo crystal field
theory and sl\an:s wilh il a cenlnl emph>s4s on lhc paU.W1>olion al metal v*nce Otbitals by lipids.
wtltle at lhc same cime scrvq as a bidac to lhe ruu molecular orhitaltr...rmcnc al compc:xes.
MThe ewl..ion ofbondina models for inorpnc complexc.t from the 1920.1o the
is
described in BaJIIo;wscn, C. J. J . Cltrm. due. 197t. J6. 194-197, lU-218. l57-l6l.
I)
396
11 Coordination Chemislr)': Bonding, Spedro, and Magne tism
Fig. 11.3 Spalial
oflhe 1\ve J lllbilals.
+z
+10
+S
+S
0 -x
+r
-s
-s
-10
-s
-:
-s
+S
+S
(b l
Fig. 11 .4 Ellron dcnsicy COCllours (or (aJ J,llll<l Cbl d.,

poiols oC maximum electron densicy. (From
428-00. Repl'oduccd with pamis.sion.J
The lrillnales u prcs<:nl
B. J. Chrm. EJUC". 1969.46.
Crystol Fllcl Tloeory
-qp--;f
I
397
.B< .
I
Fig. 11.5 Represeolation clthe d,: orbital as a linear combination of d,: : and d,:.,z
orbitals. The d,label Is aaunlly shorthand nowtlon for d-u--r
the negative field and the negative elect rons in the orilitals. If the field results from the
influence of real ligands (either anions o r the negative ends of dipolar ligands such as
NH3 or
the symmetry o f the field will be less than sphe rical a nd the degeneracy
of the d orbitals will be removed . II is th is s plitting of d orbital energies and its
consequences lhat are a1 the heart of crystal field theory.
Crystal Field Effects:

Octahedral
Symmetry
Let us cons ider first the case of six ligands forming an octahedrol complex . For
convenie nce. we may regard the ligands as beina symmetricaUy positioned alone the
axes o f a Cartesian coordina te system with the metal io n a t the ori&in. as shown in Fig.
11 .6. As in the case of a spherical field. a ll of the d orbitals will be raised in energy
re lative to the free ion because of neptive ch arge re pulsions. However. it should be
pictorially obviou5 that not all o r the orbitals will be affected to the same extent. The
orbitals lying along the axes (the d;,> and the d,:_1 :) will be more strongly repelled than
the orbitals with lobes directed betwe en the axes rthe d,1 d. ' and d:r.> The d orbitals
are thus s plit into two sets with the d:t a nd d.r'- r at a highe r energy than the other
Fig. 11 .6 Complete set of
J orbitals in an octahalrdl
field produced by oix
liganlls. The t., orilitals are

und the ,,._ orbitals
urc unshaclcd. The torus of
the d,, orbital has been
omitted for d arity.
398
11 Coordination Chemistry: Bonding, Spectra, and
..,
three. Division inlo these two groups orises from the symmetry prope.rties or
Ute d orbitals withir. an octahedral environment, which we can confirm by referring to
the character table ror the 0 1, point sroup (Appendix 0). We see that the dt and d.r-y'
orbitals transform as the ,representation and the d_,y, d", and dJI< orbit:.ls transform
as the T2, representation. Our eartier conclusion that the orbiuls are split into two
sets. one doubly desenerate and the other triply degenerate, is thus substantiated. The
labels customarily given to these two sroups also denote these symmetry pr-operties:
t'lx for the triply degenerate set and e for the doubly deaenerate pair. the lower case
being appropriate for orbitals. Of course a symmet ry analysis does not tell us which or
the two sets of orbitals is higher in energy. To determine relative orbital energies, the
nature of the interactions giving rise to the splilling must be considered.
The extent to which the e and '"!JI orbitals are separated in an octahedral complex
is denoted by A,. (the o subscript signifying octahedral) or lODq (Fig. 11.7)." More
insight into the nature of this splitting can be obtained by viewing formation of a
complex ns a two-step process. In the first step, Ute ligands appr-oach the central
metal, producing a hypothetical spherical field Which repels all or the d orbitals to the
same extent. In the second, the ligands exert on octnhedral field. which splits the
orbital degeneracy. In goil18 from the first to the second step. we find that the barycenter, or "center of gravity," of the orbitals remains constant. That is to say, the
energy of all of the orbilals will be raised by the repulsion or the advancing ligands in
step one. but merely rearranging the ligands from a hypothetical spherical field to an
octahedral field does not alter the ovl!roge energy of the five d orbitals. To maintain
Ute constant baryccnter. it is necessary for the two e11 orbitals 10 be further repelled
by 0.6A., while the three
orbitals are stabiliud to an extent or 0.4A,. ns shown in
Fig. II. 7. This constancy or the
or the d orbitals hold s for all complexes.
regardless or geometry '"
To gain some appreciation for the mllgJlitude of A., and how it may be measured,
let us consider the d 1 complex, [Ti(H 20M1 + . This ion exists in aqueous sOlutions or
Til+ and gives rise to a purple color. The si111le d electron in the complex will occupy
Fig. 11.7 Splilli"G o( the
Rve J orbitals by an
oct ahedrnl field. The
wndilion represented by
the descnernte levels on the
left is a hypothetical
spherical Reid.
the fonroal IT\IIthem;>tic:al derivation o( the dcctr06tatic

the chArJc M the
ion. the radial dist ribut ion ar the valence J
model. They depend
electrons. and the mctal-li&and olist:w:c. The factor o( 10 in IODq :>rises spccific.ally for " sinBJc
dcctroo in nn elcctrost:otic potential o( octahcdt:llacametry.
t> The tcnns D and q arc quanlitics inherent
Bec:wsc tho: electrons o( all o( the d arbihlls 111e repdlcd, il has been suucstcd that this be
rcprcsmtcdon Dtiiaa.pillina .Jioanms(suclo as r!J. lt .71by tic lines showi,. the increased or1>01
enetJY llp(ln "')ptoadl o(the lipnds. On the other hand.. alln<:tion between the metal ion and the
lipnd ions or clipolcs will rcmt in an ovcnlllawem. of CMFJY las it must if tflc complex is to be
stable! and it
umeccssary 10 incll.de all of these effects in simt* splicti,.
lone as
one is aware d their eistcnc:e.
C.ptal field Theory
399
the lowest energy orbital available to it. i.e . one of the three degenerate /'!N orbitals.
The purple color is the result of absorption of light and promotion of the tlR electron to
the e., level. The transition can be represented as
-o
The absorption spectrum of[Ti(H20)J'+ (Fig. 11 .8) reveals that this transition occurs
with a maximum at 20,300 em -I . which corresponds to 243 kJ mot- of energy for
ll.,.n By comparison, the absorption maximum" of ReF6 (also a d 1 species) is 32.500
em - , or 338 kJ mol- 1 These are typical values for 0.., and are of the same order of
magnitude ns the energy of a chemical bond.
The d 1 case is the simplest possible because the observed spectral transition
reflects the actual energy difference between the e" and r 2., levels. For the more
general d'' situation, electron-electron interactions must be taken into account and the
calculation becomes somewhat more involved. The appropriate methods are discussed on pages 433 and following.
Oystal Field
Stabilization Energy
In the ttl case discussed above, the electron occupies a t'!N orbital. which has an energy
of -0.4ll., relative to the barycenter of the d orbitals. The complex can thus be said to
be stabilizedto the extent of 0.4ll.,. compared to the hypothetical spherical-field case.
1000
ioiviclei
Wovflm8th (nm)
soo
661
3))
t.o ,---;---,, -- -- - , . - -- - - .- - r - - - ,
..
-O.S '------'-......l.----...L..--- - L -- 1 -- - '

10.000
tS.OOO
20.000
25,000
30,000
fl'<Qucnc:y (cm' 1)
Fig. 11.8 Electronic spectrum ofli 0.1 M aqueous solution o(JTi(H,Ol.J,.. The letters at the
top indicate the colors associated with pO<tioos of the visible spectrum. (From Hartmann. H.;
Schli\fer, H. L.; Hansen. K. H. An<ITJI. Alii(.
1956. 284, 153-161. Reproduced with
pe<mission.)
11
z.
It is suggested thai tile reader verify ehis equivalence by mean.s of appropriate conversion foctors.
'" Moffit!. W.; Goodman. G. L.; Fred. M.; Weimto<:k. B. Mol. Pilys. 1959,1. 109-122.
400
11 Co-dinntion Chemistrr. Bonding, Spectra, and MogMiitm
This quantity is tenned the crystal field stabilitation enu07 {CFSEJ. For d 2 and d 3
metal ions. we would expect the electrons tO obey Hund's rule and thus to occupy
different degenerate 121< orbitals and to remain unpaired . The resulting configurations.
and , will have CSFEs ofO.M., and 1.2A.,. respectively. When one more electron
it'addelio form the d 4 case. two possibilities arise: either the electron may enter the
higher energy e11 level or it may pair with anocher electron in one of the IlK orbitals.
The actual configuration adopted will, of course, be the lowest energy one and will
depend on the relative magnitudes of A0 and P, the energy necessary to c.ause electron
pairing in a single orbital. For A.,< P (the IYI!llk./ield or high spin condilion), the fourth
electron will enter one or the e11 orbhals rather than "pay the price" of pniring with
one in
orbital. The configuration will be
and the net CFSE will be
CFSE = (3
+0.4A,)- (I
+0.6A,,) = 0.6A,
(11.4)
The addition of a fifth electro n to a weak field complex gives a configuration

and
a CFSE of zero. The two electrons in the unfavorable e11 level exactly
the
stabilization associated with three in the
level (rrg. 11.9a).
If the splitting or the d orbitals is large with respect to the pairing energy (A., > P),
it is more favorable for electrons to pair in the t26 level than to enter the strongly
unfavorable ell level. In these strongfiekl or low spin complexes, the ell level remains
unoccupied for 4f through d 6 ions (Fie. I I .9b). As a result, the crystal field stabilization enugies of complexes having four to seven d electrons will be greater for strong
field than for weak field cases.
for example,lhe low spin configur.uion wiD be
giving a CFSE of 1.6Au compared to 0.6A0 for the high spin arrangement. A
summary of configurations, erystal field sl:lbilizntion energies, and numbers of unpaired electrons for d 1 throfl3h d 10 in bolh stronc and weak field situations is given in
Table 11.3.
A comparison of total energies for strong and weak field cases, including electronconfiguration will
pairing energies (P), may be computed: The CFSE for a low
be 2.4An - 3P. The corresponding hich spin configuration would have a CFSE of
0.460 - P for a difference between the two of 2.06,. - 2P. Since the two configura-
tt
I
I
-==
I
I
I
I
I
I
I
''
''
'
(b)
F;g. 11.9 Electron confi&wations of (a) a d' ion in a wealt octahedral lidcl and (b) a t!' ion in
a SlrOr1& octahedral field.
401
Td.le 11.3
d'
d2
'h
dl
11
tl
a<
tl
J'
tf'> '
J'
d'
d9
d'o
0.46.,
0.86,.
1.260
0.6A.,
0.06,.
0.46.,
0.860
I.U,,
0.6An
O.OA.,
2
3
4
e1
1.e!
'Lei
If..
This table is oomcwbat simplified becaiUC

beal nqlecled..
,.lit
11
2.R
tl.
1..
4..
ttR
tV'
ttl!
tt.e;
I
2
3
2
I
0
I
2
I
0
0.46,.
0.86,.
I .U.,
1.66.,
2.0A.,
2.4A0
I.M..,
1.26.,
0.66.,
0.0A0
eneflies and eluon-ek<:tron drts "'"""
tions differ in the spins of two electrons. this amounls to a.n energy factor of(I .Olln P ) per electron
spin.
1lle electron-pairing Cf!Cr&Y is composed of two terms. One is 1.he inherent

coulombic repulsion that must be overcome when forcing two electrons to ocA:upy the
same orbilal. A grodual decrease in the magni tude or this contribution is observed as
one proceeds from top to bottom wilhin a given group or the periodic table. The larger.
more diffuse Sd orbitals in the heavier transition metals more readily accommodate
two negative charxes than the smaller 3d otbitals. Tile second l'actor of importance is
the Joss of exchange eneray (customarily taken as the basis of Hund's rule. Chapter 21
that occurs as electrons with parallel spins are forced to have u.ntiparallel spins. The
exchange enersy for a siven con lieu ration is proportional to the number of pairs 19 of
electrons having parallel spins. Within a d subshell the greatest loss or exchanse
enersy is expected when the J ' configuration is forced to pair. Hence d' complexes
(e.g .. Mn2 and Fe') frequently arc high spin . Some typical values or pairing eneraies
ror free saseous transition metal ions are listed in Table 11 .4.
Tetrahedral
Symmetry
The two most common ge.o metries for four-coordinate complexes arc the tetrahedral
and square planar arransements. The square planar geometry, discussed in the next
section. is a special case of the more 1eneral D4h symmetry, which also includes
tetragonal distortion of octahedral complexes (page 448). Tetrahedral coordination is
closely related to cubic coordination. Although the latter is not common in coordination chemistry, it provides a convenicnl starting point for deriving the crystal lidd
splitting pattern for a tetrahedral ML4 complex.
Consider eight ligands aligned on the comers or a cube approaching a metal atom
located in the center as shown in Fig. 11 . 10. A complex such as I his would belong ta..,
the same point sroup (OIJ as an octahedral one so the d orbil.als will be split into two
desenerate sets, tlit and eR, as ror the octahedral case. In the cubic arrangement.
"The word "pair'' as wed here siml'ly means a set or l wo elearotls, net two elecuons ,.;tb their
spins paired.
402
11 Coordination Chemistry: Bonding, Spectrn, and Magneti..,.
Pairing e.-gies lor scme

3d ......,. iofts
,..
,.,
71.2 (S9SO)
81.9 (7350)
173.1 (14,47S)
213.7 (17,865)
244.3 (20,425)
301.6 (25,215)
67.3 (5625)
91.0 (7610)
120.2 ( IO.OSil)
144.3 (12,062)
194.0 ( 16,215)
237 .I (19,825)
211.6 (17,687)
285.0 (23,825)
357.4 (29,875)
13.5 (6145)
89.2 (7460)
113.0 (9450)
100.6 (8418)
139.8 (11 ,690)
169.6 ( 14. 175)
174.2 (14,S63)
229.1 (19,1Sil)
282.6 (23,625)
87.9 (7350)
100 (8400}
t23.6 (10,330)
ISO (12,400)
2 11 .5 (17,680)
2SO (20,800)
,_
Table 11.4
d"
cfl+
d'
Cr+
Mnl+
Mn2
Fe)+
d"
Mn +
Fel+
Col+
d
Fe
Co2 +
Pairirw enerJies in ltJ mot- (and cm-1) Clliculalcd from formulas and
data Jiven by Orad. L. E. J . Chrm. Phys. ms, 2J, 1119. and
J.
S. J . /norr. N11d. C/wm. 1956,1, I, 229. The vab:s pertain to the Cru
ion and may be expcdcd to be from W.4 to 30'/. sm.uer for Uw:
colnjllexcd icn u a result of the nephelauulic effect. P ..,, P.._, and PT
refer to rile coulombic, CJ<dlat\ic, and toea\ ena'JIY Dpp0$na pailinJ of
declrons.
however. the ligands do not directly approach any of the metal d orbitals. but they
come closer to the orbitals directed to the edaes of the cube (the d_... d,: and dy:l than
to those directed to the centers of the cube faces (the d:r-; and the d::l Hence the 1!11
orllitals are raised in energy while the t 11 orbit:lls are stabilized relative to the barycenter. Furthermore, since the center-of-sravity rule holds. the upper levels are raised
by 0.46 and the lower ones stabilized by O.M (Tom the barycenter, giving an energy
level scheme that is exactly the inverse of that for octahedral symmetry.
If four ligands are removed from alternate comers of the cube in Fia. 11.10. the
remaining ligands form a tetrahedron about the metal. The energy level scheme for
tetrahedral symmetry (F'tg. 11 . 11) is qualitatively the same as that for cubic. but the
spliuing (ll,) is only half as large because there are half us many ligands. The labels we
apply to the two sets or degenemte orbitals are consistent with their symmetry
Fig. 11.10 Complc:te set of
d otbituls in a cubic field.
Eilhu set of tetr:>hellr:ol
ligand$ te or 0 ) prO<llc:cs a
field one-half us strong as
the cubic field.
-x
.,.
-I
403
F;g. 11.11 Splircing of J

orbitnls in a tetruhcdrnl
1\eld.
properties in a tetrahedral environment (see the character table for the TJ point group
in Appendix D): 12 for the d""' d,: and d_., orbitals, and e for the Jx' -y' and d:' orbitals.
The g subscripts which were used for the octahedral and cubic fields are no longer
appropriate because the tetrahedron lacks a center of inversion.
The crystal field spliuing in a tetrahedral field is intrinsically smaller than that in
an octahedral field because there are only two-thirds as many ligands and they have a
less direct effect on the d orbitals. The point-charge model predicts lhat for the same
metal ion, ligands, and metal-ligand distances, a, &an. As a result, orbiml splitting
energies in tetrahedral complexes generally lll'e not large enough to force electrons to
pair. and low spin configurations are rarely observed.10 Rather, under conditions
favoring strong crystal fields, other geometries are preferred over tetrahedral
structures.
Tetragonal
Symmetry: Square
Planar Complexes
If two trans ligands in an octahedral ML" complex (for example those along the z axis)
are moved either towards or away from the metal ion, the resulting complex is said to
be tetragonally distorted . Ordinarily such distortions are not favored since they result
in a net loss of bonding energy. In certain situations, however, such a distortion is
favored because of a Jahn-Teller effect (page 449). A complex of gener.ll formula
also will have tetragonal <D.h) symmetry. For now. we will merely
consider the limiting case of tetragonal elongation, a square plamlr ML4
for
the purpose of deriving its d orbital spliUing patcem.
Figure 11. 12 illustrates the effect of
stretching on the e and ':x orbitals in
an octahedral complex. Orbitals having a z component (the d:' d.... and dy,l will
experience a decrease in electrostatic repulsions from the ligands and will therefore be
stabilized. At the same time. the "nonz" orbitals will be raised in energy. with 1he
batycenter remaining constant. The overall result is that the e., level is split into two
!zvels, an upper b 1R (dx- ,>1 and a lower a 1, (d, :) and the 12J: set is split into a b2J: (d,y)
arid a doubly degenerate eR (d,:. d_.:l Assignmenl of these symmetry labels can be
confirmed by referring to 1he D4h character table in Appendix D. The energy spacing
(d..y) and b 1, (d,.:_.') levels is defined as a. As in the octahedral case,
between the
this spliuing is equal to IODq . However, the full crystal field \lescription of the orbital
firs! e xample of" low spin lctrnhcdr.>l complex of" firs!-row Jr'ansilion metal . lelrokisllnorbornylk:oiJaii(IVI. wa$ reccnlly()C)Clfirmcd. Sec Byrne, E. K.: Rictleson. 0 . S.: Thecpdd. K. H.
Chmr. Ccmmun. 1986. 1491-t492.
20 The
404
11 Cocwdinntion Cltemistry: Bonding, Spectro, ond Maenetism
Fig. 11.12 An octahedral

c o x (u) undergoing t
al'.is elonJjltion such that it

becomes retraaoNUy
distorted (bland finally
the square planar
limic (ct. The
(d;l
Otbital may lie below che e,
(d,, and J,) Otbitals in che
square plonur
a,,
(bl
(1)
(<I
spacings for square planar complexes (and LhOse of any olhcr noncubic symmetry)
requires additional parameters, commonly labeled Dt and Ds.l '
The square planar
is favored by metal ions having a d 8 configuration in
the presence oC a strong field. This combination gives low spin complexes with the
eight d electrons occupying the low-energy d11 , dw d:' and dJCY orbitals, while the
hisfl-cnergy d..z-r orbital remains unoccupied. The
the surrounding field,
the higher the d..z-y' orbital will be raised. As long as this level is unoccupied.
however, the overall effect on the complex will be stabilization because the lower,
occupied orbitals will drop in energy by a corresponding amount. Typical low spin
square planar-complexes are [Ni(CN)J1 -, [Pd04) 1- , [Pt(NH1)Jl+, [PICJ4 J1-, and
(AuCI4
all d 8 species .
r.
Orbital Splittings in
Fields of Other
Symmetries
Although a large number of complexes can be accommodated under the symmetries

that have been discussed, there are o.lso many that exist in other seometric configurations. These configurations will not be treated in detail, but their d orbital energies are
included in Table II .S along with energies for the more common seometries. From the
values in the table , energy level diagrams similar to those given previously for
octahedrnl. tetrahedral. a.nd square planar complexes can be tonstrucled for any or
the symmetries listed.
Factors AHecting the There are a number or factors that affect the extent to which metal d orbitals are split
by surrounding ligands. Representative values of ll for a variety of complexes are
Magnitude of 6
Larger +ve charge implies
greater interaction with the
ligands.
listed in Table 11.6. From the data several impartan t variables and trends can be
identified.
Oxidation state q{ tloe metal ion. The magnitude oC ll increases with increasing
ionic charge on the central metal ion. Several complexes in Table 11 .6 involving
different oxidation states for a particular metal ion with the same ligand illustrate this
trend . Note, for example, [Ru(H 20JJ '+ (ll0 19,800 cm- 1) and [Ru(H1 0)J1 + (ll0 = 28,600 cm- 1).
Nat11re of the metal ion. Significant differences in ll also occur for analogous
complexes within a given group. the trend being )d.< 4d < Sd. In progressing rrom Cr
21
SeWfer. H. L.: Glianann. G_ BOJk Prirodplrs ofUtllNI Find ThNry; Wiley-ll'lla'Sc:icnce: New
yen. 1969: pp 6l-6.S aod )4}-)47.
405
Qoystal Fie ld Tlteory
Tallie ll.S
The ....,SlY levels of J
otl>italo In crystal fields of
dilfe<enl sym,.tries,..
c.N.
l
2
3
4
4
5
5
6
6
7
8
8
9
12
Struc:ture
Unearc
U near<"
TrisooaJd
T ettahedral
Square planar"
T risonaJ bipyramidal
Square pyramidal'
Octahedral
Trigonal prismatic
Pentagonal bipyramidal
Cubic
Square antiprismatic
[ReHJ1 - structure (see Fe. 12.40)
Icosahedral
d,.o
d,.t_l.
S.l4
10.28
-3.21
-2.67
- 4.28
7.07
0.86
6.00
0.96
4.93
- 5.34
-5.34
-3.14
-6.28
5.46
-2.67
12.28
-0.82
9. 14
6.00
-5.84
2.82
-S.34
-0.89
- 0.38
0.00
-2.2S
0.00
J.,.
- 3. 14
-6.28
5.46
1.78
2.28
-0.82
- 0.86
- 4.00
-S.84
2.82
3.S6
- 0.89
-0.38
0.00
J,..
cl,.
O.S7
O.S7
1.14
1.14
-3.86 -3.86
1.78
1.78
-5. 14 - 5.14
- 2.72 -2.72
- 4.S7 -4.S7
-4.00 -4.00
S.36
5.36
- S.28 -5.28
3.S6
3.S6
3.S6
3.S6
1.51
I.S I
0.00
Zuckerman. J. J. J. CMm. Elluc. t965. 42. liS. Krishnat!WC"Itly. R.; Schup. W. B. J. Chmt.
Edur:. 1!169. 46. 799. Used with pcnniuion.
All ma-gics are in Dq units; IODq A,..
r l.ipnd$ lie alone
axl$.
l.iJands lie in zy plane.
Pynmid base in zy plane.
Ligand ligand repulsion

decreases.
to Moor Co to Rh. the value oft:.,. increases by as much as SO"/.. Likewise. the values
for lr complexes are some 25% greater than for Rh complexes. An impoctanl resull of
this trend is that complexes or the second and third transition series have a much
greaJer tendency to be low spin than do complexes of the first transition series.
Number and geometry of the ligand!. As we have seen. the point-charge model
predicts that t:. for a telrahedral complex will be only about 50"/. as large as for an
o ctahedral complex. all Olher factors being equal. This approximate relationship is
observed for VCJ4 and (VCJ6 )1 - . as well as for (Co(NH 3)4 )1+ and [Co<NH 3),J 2 +.
Nature of the ligands. The effect of different ligands on t he degree of splitting is
illustrated in Fig. 11. 13. which shows the absorption spectra of three CrL" complexes.
Three d-d transitions are predicted for each one. based on an analysis that includes
the effects or electron-electron repulsion (see pages 433- 437J. The transitions labeled
" correspond to t:.n or IODq. Note that there is a steady increase in the frequency of
this absorption as the ligating atom changes from F to 0 to N. correspo nding to a
progressive increase in the field sltenarh. Based on similar data for a wide variety of
complexes. it is possible to list ligands in order of increasing field strength in a
spectrochemical series. Although it is nOl possible to form n complete series of all
ligands with a single metal ion, it is possible to construct one from overlapping
sequences, each constitutinJt a portion of the series:n
1- < Br- < S1 - < SCN- < Cl- < N). r < urea. OH- <ox,
2 < NCS- < py. NH3 < en < bpy. phen < NOi < CHi".
C6Hs< CN- <CO
oz- < H 0
Z2
Allbrevialions are ox
pbec
oxa1ale. py pyridine. en ethylenediamine. bpy 2.?-bipyridine.

For SCN- and NCS- . the bclund atom is Biven lint. Lever. A. B. P.
ln<Kfuttic Eltrottk
2nd ed.; Elsevier: New Yoril. 1986. J..-gcnsen. C. K. Modnn
As,.cts of UtcmJ Fidd TMory. Elsevier: New Yoril. 1971:
a
406
11 c ..... dination Chemistyy: Bonding, Spectra, and Magnetism
Tablell.6
Same val"" af
transition .,.....
lor
...
Oloidoriooo state
Complex
af _,...
(VCIJ'-
4
4
4
VCI4
[CrFJ[CrPJ'[CrtH20)J3+
[Cr(en),J'
[CrtCN),_f[Mo<H:zO)J 3+
[MnFjrrcF,i[ReFtf[Fe(H2
[Fe(ox),J'-
o>J'
3
3
3
3
3
4
4
4
3
3
3
[Fe(CN)j-
o>J'
!RutH1
[Ru(ox>,J'[Ru(H:zO),j
(Ru(CN>.f(CoFJ[CoFJ'[Co{H2 0)Jl+
[Co{NH,).f
3
3
2
2
4
]
3
3 3
[Co(H:zO>J+
[Co{NH,>J2 +
[RhFJ2 (Rh(H 20).J,.
[Rh(NH,JJ 3
(lrFj(lr(NH3)J'+
2
2
2
4
3
3
4
3
/;.(em- ')
OA
ls.400
OA
22,000
r.,
oh
oh
o.
oh
o.
o.
o.
o.
o.
o.
o.
o.
o.
o.
o.
o.
o.
o.
o.
o.
o.
o.
o.
IS.060
17,400
22,300
26,600
26,000
21,800
28,400
32.800
14,000
14,140
3S,OOO
32.200
28.600
28,700
19.800
33.800
20,300
13.100
20.760
22,870
23,160
9200
10,200
S900
Ttl
o.
o.
o.
o.
o.
" Le..,... A. 8 . P. lfiOtllunlc

Ebcvier. New Yor!<, 1986; Chapters 6111ld 9.
h
7900
20.SOO
27.200
3-4.100
27.000
41.200
2nd cd.;
Abbreviations: ox - onlale: en - elhylencdi11minc.
Js&rgensen has developed a means of estimating the value or t. for an octahedral

complex by treatina it as the product of two inllependent factors:U
t..,
= fg
(11.5)
'The quantity f describes the field strength of a ligand relative to water. which is
assigned a value of 1.00. Values range from about 0. 7 for weak field bromide ions to
V
JllrJCnSCrl. C . K. Mod"" " -<fl ofU,atttl Filld
Elsevier: New Vorl<, 1971; Ch:>pt..- 26.
C..ystal Flelcl Theoty
F;g. 11.13 Speccra of' chm:
F<tqUC1'CY(<111' 1J
IG.OOO
:O.OOCl
JO.OOCl
407
40.000
c:tlromium( Ill) comple:<eS:

(a) (Cnen>,J': lbl
(Cr1oxhJ'-; (c) (CrF.J'-;
corresponds to A,,;
CT c.harge cransfer bGnd
(:see page 45S). The
coordinulin& :uoms for 1he
bidcnlule ethylenediamine
(en) and oxalule (ox)
u"' N and 0,
"'Spcelively. (Spec!ra a and
b from SchiUfer, H. L.
Z. Phys. CAI'm.
om Main) 1957, //, 6S.
Reproduced with
permission. Spec!rum c
sketcl1ccl from daca given
(ot
..,.,
t
fb i
Jraensen-c. K .
Alnorption Sprctra and
CMmical Botrdinx in
Pers;unon:
Elmsford, NY, 1962.)
.. _,
I<)
lOO
soo
kJ mor 1
uboul I. 7 for the very strong field cyanide ion. The n facror is characteristic of Ihe
metal ion and varies from 8000 to 36,000 em- (Table II. 7). Equation II.S is useful for
approximating A and. in combination with pairing energies (Table 11.4), for predicring
whether a new octahedral complex will be
or low spin.
Although the spectrochemical series and other trends described in this section
allow one to rntionaliz.e differences in spectrn and permit some predictability. they
present serious difficulties in interpretation for crystal field theory. If the splitting of
the d orbitals resulted simply from the effec t of point charges (ions or dipoles). one
should expect lhat anionic ligands would exert the areatest effiecl. To the contrary,
most anionic ligands lie at the low end of lhe spectrochemic:al series. Furthermore,
OH- lies below the neutral H:O molecule and NHJ produces a areater spliuing than
H1 0, although the dipole moments are in the reverse order II'NH. ,. 4.90 x 10-JO
C m; I'H,o = 6. 17 x 10-JO C m). The model is also unable to account for the fact that
with certain strong field ligands (such as CN- ). A, varies only sliahlly for anaJosous
complexes within a group. 'These apparent weaknesses in the theory called into
question the assumption of purely electrostatic interactions between ligands and
408
11 Cao<dination Chemistry: Bonding, Spectra, and Magnetism
Table 11.7
Selected values of/ and g
factors
ligand
I fact
Metol ion
gfoct....
Bf
0.72
0.73
0.78
0.83
0.9
0.99
1.00
.1.02
1. 18
1.23
1.25
1.28
1.33
1.7
Mn(ll)
Cr(lll)
Co( Ill)
8.0
8.7 .
9
12.0
14.0
17.4
18.2
Rll(JI)
20
Mn(IV)
Mo(lll)
23
24.6
27.0
30
32
36
sew
ClwJ
Fox = C2
o;-
H 20
NCsglyNH2CH1 COi
py = C.sH,N
NH,
en = NH1CH2CH2 NH2
bpy = 2.2'-bipyridine
cw
Ni(ll)
Co{ll)
V(U)
Fe( Ill)
Rh(lll)
TqiV)
lrtlll)
Pt(IV)
C. K. Modn7o As{Hcts of Ugund

Thn>ry;
Else.Xr: New York, 197t; Chapler 26.
h In units o( kK ( 1000 an-). Liplinc aloma are shown in
"
boldfou: lypc.
central metal ions and led eventually to the development of bonding descriptions that
include covalent interactions between ligands and metal. Despite its imperfections. the
basic crystal field theory can be used to interpret a number of effects in coordination
chemistry, several of which are discussed in the next section.
I
Applications of
Among the early successes of crystal field theory was its ability to account for
magnetic and spectral propertie.s of complexe.s . In addition, it provided a basis for
understanding and predicting a number of their structural and thermodynamic proper
ties. Several such properties are described in this section from the crystal field point of
view. Certainly other bonding models, such as molecular orbital theory. can also be
used to interpret these observations. Even when they are, however. concepts from
crystal field theory. such as crystal (or ligand) field stabilization energy. are often
invoked within the discussion.
One of the first indications that crystal field stabilization energy might be important in transition metal compounds arose from the computation of lattice energies. We
have seen in Chapter 4 that, although the prediction of lattice energies is not highly
accurate, such predictions are much better for ion.s such as Na+. K + .
+. Mn2 +,
and Zn2 .. than they are for c.Z+. Fe2 , Co2 . Ni2 +. and Cu2 +. Wherever a serious
discrepancy for a six-coordinate metal ion is found, it may be attributed to the CFSE.
The ions that do not show such discrepancies are those with tfl. d 5 (high spin), and d 10
configurations, which all have in common that CFSE = 0. Consider the lattice
energies of the halides from CaX 2 to ZnX2 in which the metal ions occupy octahedral
holes. Inasmuch as we might expect a gradual decrease in ionic radius from Ca1 + to
zn2+ (Chapter 2). we should also expect a gradual and smooth increase in lattice
energy based on the
equation (Chapter 4). However, as shown by
Fig. 11.14. the expected smooth curve is not observed. The ions Ca1 +. Mn2 +. and
Zn2 + lie on a curve that is nearly a straight line. Moreover, deviations from this
approximate line are maximized in two places: in the region of yt+ and the region of
Nit+. Table 11.3 indicates that for a weak octahedral field (recall that the halide ions
Crystal Fielcl Theory
409
Fig. 11.14 Lattice energies

d the divalent metal halides
of the first transition series.
Verticul bars indicate
3000
uncertainties in
experimental values.
(Modified from George, P.;
McClure, D. S. Prog.
l1SO
lnorg.
1959, I,
381-463. Reproduced with
permission. I
...
:::.
2500
are on the weak end of lhe spectrochemical series), V2 + (d 3) and Ni2 +(d 1 ) have the
d 1,
ions have somewhat Jess (0.6and
greatest CFSE values ( I.U,). The d 2,
0
10
0.8ll.,) and the d d', and d cases have zero CFSE. qualitatively confirming the
shape of the curve within the unfOC'tunately large experimental errOl'S.
Somewhat beller data are available for lhe enlhalpies of hydration of transition
metal ions. Although this enthalpy is measured at (or more properly, extrapolated to)
infinite dilution, only six water molecules enter the coordination sphere of lhe metal
ion to form an octahedr:ll aqua complex. The enthalpy of hydration is thus closely
related to the enthalpy of formation of the hexaaqua complex. If the values of ll.Hhyd
for the + 2 and + 3 ions of the first transition elements (exeept &;Z+. which is unstable)
are plotted as a function of atomic number, curves much like those in Fig. 11.14 are
obtained. If one subtracts the predicted CFSE from the experimental enthalpies. the
resulting points lie very nearly on a straight line from Ca2 to Zn2 + and from 52 to
Fe 3+ (the + 3 oxidation state is unstable in water for the remainder of the first
transition series). Many thermodynamic data for coord ination compounds follow this
pattern of a double-humped curve, which can be accounted for by variations in CFSE
wilh d orbital configuration.
A slightly different form of the typical two-humped curve is shown by the ionic
radii of the 3d divalent metals. These are plotted in Fig. I I. IS (from Table 4\4). For
both dipositive and tripositive ions there is a steady decrease in radius for the strong
field case until lhe
configuration is reached . At lhis point the next electron enters
the e6 level, into an orbital directed at the ligand.s. repelling lhem and causing an
increase in the effective radius oflhe metal. In lhe case of high spin ions the increase in
radius occurs with the .. configuration for the same reason.
tt,
41 0
11 Coordination Chemistry: loncling, Spectra, ancl Magutlsm
or
120
:g90
Fig. 11.15 Radii I he

divalent ions Cu>+ to Znl+
(above) and the trivalent
ions &?+ to Gal+ (below)

as a function or the number
of d electrons. Low spin
ions are i ndiCIItcd by solid
circles. [Data from
Shannon, R. D.; Prewitt.
C. T. Acta Cryst. t970,
60
826. 1076.1
90
The crystal field model cnn also be used to account for the stability of particular
oxidation slates. In aqueous solution CO( IJI) is unstable with respect to reduction by
water to form Co(ll). Although there are several energy terms involved, this may be
viewed as a reflection of the high third ioniution energy of cobalt. If various
moderate-to-strong field ligands are present in the solution, however. the Co(lll) ion is
perfectly stable. In fact, in some cuses it is difficult or impossible to prevent the
oxidation of Co( II) to Co(ll1).
For example, the appropriate emfs (in volts) are
[Co<H 20l,JZ+----+
(CO(ox>,t- --+
E o= - 1.83
e-
eo=
e-
[Co(phenhl2+----+ [Co(phen>i+ + e[Co(edta)) 1 - --+ (Co(edta))- + e2
----+
[Co(NH,>J,.. + e-
+ CN - - - - [Co(CN),J1 - + H 10
-0.57
(11.7)
Eo= -0.42
(11.8)
Eo= - 0.37
(11.9)
Eo= -0.18 (11.10)
[Co(en)lJ + ----+ [Co(en),J'+ + e[Co(NH,),)1 +
(11.6)
e-
eD=
eD=
-0.11 (11. 11)
+0.83 (11. 12)
Note that the order of ligands in Eqs.

is approximately that of the spectrochemical series and hence that of increasing crystal field stabilization energies. The
Cr,sta l Field Theooy
411
oxidation ofCo(JI) to Co( Ill) results in a change from high to low spin. We can think of
the oxidation as taking place in two steps, the first being the rearransement of
electrons to the low spin state and the second the removal of the eR electron to
produce Co(JII}:
---+
---+
This is not to imply thnt the process actually occurs in this manner, but we may
consider the thermodynamics as the sum of this hypothetical sequence. The first step
involves pairing of electrons, and the energy required for this will be in part compensated by the additional CFSE of the low spin configuration ( 1.86,. versus 0.86,.). The
stronp:r the fidd , the larger will be the magnitude of 6 ,.. The second step, removal of
an electron from the eR level, is endothermic because of the high ionization energy
(Co2 to eo'}. but the increase in CFSE (1.86,. to 2.46.,) will favor ioniution. It
should be pointed out that CFSE is only one of a number of factors affecting the emf.
In particular, entropy effects associated with chelate rings can be important and are
largely responsible for the fact that the order of lipnds in Eqs. 11.6-11. 12 is different
fTom that in the spectrochemical series. In any event. the emf of a couple can be
"tuned" by varing the nature ofthe ligands, a phenomenon that becomes exquisitely
important in biOlogical systems (see Chapter 19}.
Crystal field factors may also be used to help account for observed site preferences in certain crystalline materials such as the spinels. Spinels have the formula
AB2 0 4 , where A can be a Group llA (2) metal or a transition metal in the + 2 oxidation
state and B is a Group IliA (3) metal oro transition metal in the + 3 oxidation state.
The oxide ions form a
cubic lauice with eigh t tetrahedral holes and four
octahedrnl holes per
unit. In a so-called normal spinel such as
the
t.tgl ions occupy one-<ighth of the tetrnhedral holes and the All+ ions occ.upy onehalf of the available octahedrnl holes. This is the arrangement that would be predicted
to be most stable inasmuch as it yields a coordination number of 4 for the divalent ion
and 6 for the trivaknt ion (cf. [Be(H 20)4 )2 + and [AI(H 20)J'+, page 393). Very
interesting, therefore, are spinels havina th e inveru structure in which the A(JI) ions
and one-half of the 8(111) ions have exchanged places; i.e., che A(ll) ions occupy
octahedral holes along with one-half of the 8(111) ions while the other one-half of the
8(111) ions are in tetrahedral holes. Also observed are cases that are intermediate
between the normal and inverse distributions. It is common to <lescribe the structure
of a spinel by the p-.u-umeter A, defined as the fraction of 8 ions in
holes.
The value of A ranges from zero for normal spinets to O.SO for t.h ose havinsthe inven:e
composition. Cation distributions (as A values I in a number of common spinel.s are
given in Table 11 .8.
T..W. l UI
Valotes al A lor opinels,
0
0
0
0
us
0
0
o.s
0.1
-:-
; Wells, A. F. S trw:turol
.o."'
t- .--:
0.38
0
o.s
"o "
o.s ..
o.s
.
I
0
0
0
0
CllmtUtry, $th eel.: Clarendon: O><fonl . 1986; pm. UM<I
_.:'Ji i. i : G-
.1 ..
0
0
.- .._
..,
.s. :. ! 1-.:..: ..il
412
11 Caordinali- Chemistry: Bonding, Spectra, and Magnelism
Several factors undo ubtedly play a role in determining whether an oxide

the nonnal or inverse spinel structure. one or which is d orbital splitting energy.
Although the CFSE contribution to the total bonding energy o r a system is only about
S-10"/o, it may be the deciding factor when the o ther contributions are reasonably
constant. The crystal field contribution for spinels can be assessed by considering the
difference in crystal field stabilization energies for octahedral compared to tet rahedral
coordination for the metal ions involved. For purposes or estimating this difference, it
can be assumed that the oxide ions will provide a moderately weak crystal field similar
to that for water, for which a number of l:J.,. values have been measured . Values of l:J.,
for the four-coordinate sites can be approximated by the relationship l:J., = al:J..,.
Octahedral site preference energies detennined in this manner for di- and trivalent ions
the first transition series nre give.n in Table 11 .9.
Table 11 .8 reveals that most spinels involvina Fe 3
have the inverse
structure. The dj Fe3 ion will have a CFSE of zero for both tetrahedral and
octahedral coordination, so if there is to be a site preference it will be due to the A(IJ)
ion. This is clearly the case for
for example. the Ni2 + ion having an
octahedral site preference energy of 86 kJ mol- 1 In mngnetite. Fe 30 4 , both A and B
ions are iron. with some in the + 2 oxidation st:lte and others in + 3: Fe 11 Fc: 111 0 4 For
the tf' Fe2 + ion, oclahedral coordinat ion is more favorable than tetrahedral by about
IS kJ mot- . which, allhouBh only a modest amount, is a pparently sufficient to invert
the structure. In contrast. the similar o11ide Mn30 4 has the nonnal structure. ln this
instance, the ds Mn1 has no CFSE in either octahedral or tetrahedral fields, but d'
Mnl+ shows a preference
106 kJ rnol- 1 for octahedral sites . For Co3 0 4 another
mixed-valence oxide, there is an :1dditional factor to take into account-Co' is low
or
or
Table 11.9
Cry>tal rreld data for aqua complnots of -..1 ions in ""' lint lrOIIIition ....
me
Octohedrol
field
configuration
No. of J
elect.ono
I
2
3
4
.5
6
7
..
....8
Tc'+
zo
yl+
'F
Chapler6.
" J
tV!
rrl
'D
CoJ+ '
coz I
Nil+

rt!
l!ltl
l!ltl
tl,.e!
s
s
Fe1
.-2t!
tL
p ;:
lpl
zo
,. .1! <:..f0_
- 1. ' 1.r.
tl.r.
, .
>.
rlti
20.100
19,9SO
12,1 00
17,400
14.000
2 1.000
. 7500
14.000
9350
r'
20,760
9200
8.500
12.000
'
Tetr.
(kJ _,_.,
8930
8870
S380
7730
6220
9330
3330
6220
4 160
96.2
190.9
174
2SO
10 1
lSI
0
0
44.7
64.1
127
SI.S
74.0
29.8
44.6
0
0
29.9
32.1
64
122
176
71
106
0
0
14.8
4090
88.0
122
86. 1
.58.7
36.2
29.3
86
60.6
...
_r
...
......t..
.
Oct.
configuration
e'
tl211
(kJ _.....,
field
1!1
4p
4p
'D
jD
yl+
crl
cr
Mnl+
Mnu
FeJ+
CIJ2+
,.
'(i. ....
... -
,._
.
CI>CIJY 1101 calallalcd bcCaulc
Octoheclrol
site preference
CFSE
Tetrahedrol
3780
.SJ30
.I
.{
..
i'/::.T. t..J:
It.low
.
-+
. ,,_, . . ,. .... ;
25.5
:- "'r - - '": -,-
'
, . '
.:
Mole ... la r Orbital Theory
41 3
spin in the field produced by six oxide ions.

makes for complications in estimating
an octahedral site preference energy for Co'+ because in a tetrahedral site it would be
high spin. However, the low spin tf' configuration imparts additional stabilization to
Co3+ in an octahedral hole. Thus the octahedral preference for Col+ will clearly
outweigh that for
(29.3 kJ mol- 1), favoring the normal arrangement.
Although c rystal field theory quite successfully rationalizes observed structures
of the spinels of the first transition series. it must be applied with care to other
examples. In comparing structures in which other factors (ionic radii, covalency. etc.)
a re more dissimilar, d orbital splittings alone generally do not explain the observations. In these cases, a broader analysis is required.
Molecular Orbital
Theory
Although the crystal field theory adequately accounts for a surprisin&IY

quantity
of data on transition metal complexes, the theory has serious limitations. There are
several experimental and semitheoretical arguments that can be presented against the
assumption that the splitting of mebl d orbitals is a result solely of electrostatic effects
and that the bonding between metal and ligand is ionic with no covalent character.
Indirect evidence that electrons are shared between the ligands and the central
metal ion comes from the nephtlauutl'c (j/tct. It is found that the elect.r on-i:lectron
repulsion in complexes is somewhat less than that in the free ion. From data derived
from eJectronic speCtra of complexes, separate nephelauxetic series may be set up for
metal ions and for ligands, indicatins the order of decreasing elect ron-electron repulsion (or increasing nephetauxetic effect) (Table 11.10). The observed decrease in
electronic repulsion that occurs upon bond formation may be attributed to an effective
increase in the distance between electrons that results when metal and ligand orbitals
combine to form larger molecular orbitals. (Nephelauxetic means "cloud expanding.") The ligands that are most effective in delocaliz.ing metal electrons display the
largest values of the nephela u xetic parameter, h.
Table 11.10
The nephelauxetic series of
ligands and -"" ions
Ugoncl
"
0.8
H 20
urea
NH,
J.O
en
ox
I.S
I.S
2.0
2.1
2.3
2.4
2.7
acw
Br-
N-l
.-
1.2
1.4
Metol
Mn(IJ)
V(ll)
Ni(ll)
Mo(IJI)
Cr(lll)
Fe( Ill)
Rh(lll)
lr{lll)
Co(Ill)
Pt(IV)
Pd(IV)
"
0.07
0. 1
0.12
O. IS
0.20
0.24
0.28
0.28
0.33
0.6
0.7
The lelal nepbelauxelic clrecl in a
hx t.c.
""""'""-"-"'""""'
j
product
Po< lipnd
allbrevi:lrions. see Tat>le! 1.1.

C. K. Ollldutlon NumiHr.
IJIId Ozldotio11 Stain-;
New
vcn:
P
w0
., ]
..
414
11 Coordination Chemis1ry: Bonding.
and Magnetism
Additional evidence for covalency in

bonds is provided by electron
paramagnetic resonance (EPR). As a result of their spios, unpaired electrons behave
like magnets and align themselves either parallel or antiparullelto an applied magnetic
field. These two alignments will have sligh lly different energies, and transitions from
resonant energy in the
one level to the other can be induced and detected by
form of electromagnetic radiation. An unpaired electron that is not subject to interactions with other unpaired electrons or with magnetic nuclei will show a single absorption for this t.ransition. The EPR spectra of many complexes. ho wever, show
hyperfine spliuins pattems that arise from the interaction of the unpaired metal
electron with magnetic nuclei on the ligands (F'tg. 11.16). This clearly indicates that the
electron is at least partially delocaliz.ed over the ligands.
Octahedral
Complexes
The construction of molerular orbitals for an octahedral complex involves the same
seneral approach that was used in Chapter S for simpler molecules and ions. In the
case of the complex, there will merely be more overlappins orbitals and electrons to
the valence orbitals available on
consider . For a complex ion such as
the central metal will be the 3d, 4.f, and 4p. The ligand orbitals involved in u bonds to
the metal will be the six approximately sp' hybrid lone pair orbitals on the ammonia
molerules. (For 1r-bonding ligands, additional orbitals would have to be considered.)
Although it may at first appear that findina the proper linear combinations of nine
metal orbitals and six ligand orbitals would be a formidable task, we can draw on ooc
previous experien<:e, which has shown lhat usina the symmetry properties of the
orbitals sreatly expedites the procedure .
Since the molecular orbitals we are seekins will be linear combinalions of metal
and ligand atomic orbitals havina the same symmetry, it is appropriate to begin by
constructing linear combina1ions of the ligand orbitals, or ligand group orbi1als
(LGOs). that will overlap with metal orbitals along the octahedral bonding axes.
(Recall that this approach was used previously for BeH2 and NOi' in Chapter S.)
These LGOs must match the symmetries of the metal orbitals available for bonding.
As has already been stated, the melal valence orbitals or interest ure the n3, np . and
(n - I )d. Their symmetry properties in an octnhedral complex can be determined by
character table (Appendix 0). which reveals that the s orbital
reference to nn
transforms as a 1, and the set of p orbitals as t whereas the five d orbitals lose their
degeneracy to forme, <dt and d.r-,;> and ' !x (dY' d,: and dy:) sets. (Note that these
two groups of d orbitals are the same as we saw previously in crystal field theory.)
In order to actually participate in a u bond within the complex. a metal orbital
must be capable of positive overlap with a ligand group orbital directed along the
bond ina axes. For I he moment. let us merely consider the directional requirement and
o,
Fig. 11.16 The electron
pur.amugnelic
s;pecrrum or K, lrCJ. in
K,PrCJ.. (From Owen. J.
FD,>duy Dist:. Cltrm. Sut:.
t9SS, 19,
Reproduced wirb
permission.I
415
ignore the fact that for positive overlap. the metal and ligand orbitals must also have
the same sign. The o 1,. metal orbitnl will be spherical, therefore being capable of
overlapping with LGOs on all axes. The 11u and t 11 sets all have lobes concentrated
along the bond directions and thus also are capable of bond participation. This is
shown in Fig. Jl.l 7a for the d,r-y> orbital. The l 'l.Jt set, however, will have lobes
directed between the bonding axes and thus will yield no net overlap with ligand
orbitals (Fig. 11.17b).
The foregoing analysis ha.s shown that the LGOs to be constructed for the a bonds
of an octahedral complex must be of u 11,., and I!" symmetries. The same conclusion
could have been reached in a more for mal manner by considering the six u bonds of an
octahedral complex as vectors (Ftg. 11.18) and detennining how they transform under
point group. (For a review of the procedure
the symmetry operations of the
involved, see Chapter 3.) The reducible repre.s entation, r "' that results from counting
the number of vectors that remain unchanged by each symmetry operation is shown in
11.18. Reduction o r this representntion (Eq . 3. 1) yields o 1,.., rM. and 11,. as its
irreducible components. indicating that these arc the symmetries of the metal and
ligand group orbitals that will be suitable for formina a molecular orbitals in the
complex-the same conclusion reached earlier by considering the capability of the
metal valence orbitals for overlap.
Dctennining the symmetries of the orbitals that will participate in Lhc bonding
does not tell us what specific combinations of ligand lone-pair orbitals should be used
in constructing Lhc six LGOs.!A Some insight into this process can be obtained from
Ftg. I 1.19. The sign or the wave function for the metal u111 orbital is everywhere the
o,.
,.
,.
Col
(b)
d,,_,..
Fig. 11.17 Overlap of ligand orbitals in the xy plane with metal

(al tLnd J,.. lbl orbitals.
Note that an appropriate choice of sign for the lipnd otbitllls provides positive overlap with
the
orbital; however, no q c sisn choice for the licand wave function produces
positive overlap with the J_.. orbital.
d,,_,,
this is ,.,.,.,.y
with projection operators. For a
dilasssion of lhis method, see lhc ....,.., theory tots li$tcd in Footnote I of Olapter 3.
1 Within a IJOUI!thecmtical ualylil,
416
11 eo-dination Chemistry: B011diog, Speetra, 011d Magneti1111
L
L/'L
L+--M --+L
L,/
L
r.,
r.,
.
.
o.
a,,
8'1
6C,
3C! (
Jo
0
60.
2
'J
Fig. 11.18 Jdencilication of rhc symmetries of lipnd croup otbiluls and meral otbilals
involved in rhe u bonds (represenrcd as vecrors) of un ocruhedral ML.. complex. The
characu:rs rlrhe reducible rcpresencorion.,r are derived by counrina rhe number rl vec1ors
rha1 remain unmoved under eadl symmelry operation o( the 0 11 point IIJ'OUp. The irreducible
componems of r . are obluincd by applica1ion of Eq. 3. 1.
R9- 11.19 Ligand IVOUP otbitals (l.GOsl und

appropri:ue for u bondina in an ocrahedral ML,. complex.
meral :uomic orbirals
same, which is taken to be positive. The six ligands can interact equally with this
orbital. and each conlributina orbital must also have a positive sian. Thus the a 1, LGO
can be constructed from an additive combination of the six ligand orbitals:
1:......
..
+ a_" + uy + u _Y + u: + u _, )
(11.13)
where 1: and u represent the wave funclions for the ligand group orbital and lhc
contributing ligand orbitals, respectively, and 1/6 is a normalization constant. The
Molecular O<bital Theory
LGO that can interact with the d,r- y

andy axes:
I,r-y
l(u_.
417
will huve components only along the x
+ u __, - uy - u_:)
(11.14)
The LGO that matches the d::- metal orbital is
I:'
o:
-da<z.:r< + 2u_, -
u_, - u __. - u,. - u _1 )
(IJ. JS)
The three LGOs of r 1,. symmetry that will overlap with the metal p orbitals arc
constructed in a similar manner. as shown in Fig. 11 . 19. S ince the metal
orbitals
cannot participate In uoverlap,they are considered non bonding molecular orbitals in
com plexes where there is no possibility for .,. bonding. In cases where there are lipnd
orbitals of appropriate symmetry available. the t lJt orbitals will be involved in., bonds.
A molecular orbital energy diagram for the u bonds in an octahedral complex such
as [Co(NHJlJ3 + is shown in Fi&. 11 .20. There are several approximations involved
and the diagram shown is only qualitatively accurate; even the o rderina of the energy
levels is somewhat uncertain. However, this does not detmct from lhe usefulness of
the diagram. It is cenain that the overlap of the metal 4s and 4p orbitals with ligand
group orbitals is considerably better than that of the 3d orbitals .:!:! Consequently. the
fig. 11.20 A a-bond molecular orbital diaaram
ror a C4mplex of octalledrol "Yl'lmetrY.
n In acneral. d otbilals tend to be llqe and dilfuse 111111. as a resull. owrlop of d orbitals with olhen
may be qutllllitat/ffl;, poo. even wbal qualitUJiwl] ravonllle. This
is
in Chapt..- 1&.
418
11 Coordination Ooemistry: loading, Spec1ra, and MngnetiJm
1,., molecular orbitals are the lowest in eneray and the corresponding and
antibonding orbitals the highest in enerJY . The e11 and orbitals arising from the 3d
orbitals are displaced less from their burycenter because of poorer overlap. The 12>1
orbitals, being nonbondins in a cronly system, are not displaced at all from their
original energy.
Electrons may now be ndded to the molecular orbitals of the complex in order of
increasing enersy . For [Co<NH,)hlJ+ there will be a total of eighteen electrons to
assign, twelve from lone pairs on the ammonia ligands and six from the 3dto configura
lion of the Col+ ion. The electron configuration of the complex can be represented
or in a more abbreviated form as simply 1t,. Note that [Co(NH1)JJ+ is
diamagnetic because electrons pair in the r111 level rather than enter the higher energy
level. If the energy difference between the
and levels is small, as in [CoFJ' - ,
the electrons will be distributed t;_.e; 1 Thus both molecular orbital theory and crystal
field theory account for magnetic and spectrol properties of octahedral complexes on
the basis of two sets of orbitals separated by an energy gap 6n. If this eneray gap is
greater than the pairing energy. low spin c.o mplexes will be formed, but if the energy
necessary to pair electrons is greater than 6n high spin complexes will result.
u,JI and
e;
Tetrahedral and
Square Planar
Complees
e;
e;
The procedures used in the precedins sect.ion may also be applied to the ge.n eration of
MO diagrams for
of other geometries. The metal atom or ion in each case
will have the same nine valence orbitals available for bonding, but their symmetry
properties will vary from one geometry to another. For a tetrahedral ML4 complex (T4
symmetry), the metals and p orbitals have u 1 and 11 symme tries. respectively (see the
T4 character table in
0). The five d orbitals a re split into two sets: e
and
d.r-,rl and 12 (d_.,, dr.. and d,..l. The four LGOs constructed from ligand lone-pair
orbitals will consist of a t 2 set and one orbital of a 1 symmetry. The
LGOs can
interact with both sets of metal 12 orbitals (p and d) to &ive three sets or cr MOs-one
bonding, one slishtly antibonding, and one clearly antibondina.
A cr MO diagram for a tetra hedral complex is shown in Fig. 11.2 1. Note that in
contrast to the octahedral case , the metal e o rbitals are now nonbonding. The separation between the e and the next hi&hesl 11 orbitals is labeled 6,. as in crystal field
theory. For a
such as [CoCI4)2 -. the ligands provide two electrons each for a
total or eisht. and the d 1
ion furnishes seven, givins an overall total or fifteen.
Twelve electrons will fill the six lowest energy molecular orbitals (through the t: set)
with the final three electrons remaining unpuired and occupying the slightly lllltibond
in&tl molecular orbitals.
A number of four-coordinate c.o mplexes adopt a 5quare planar seometry. which
for four identical ligands. leads to
symmetry. In this environment, the metal d
level is split into a 111
e11 (dr.
b2>1 (d...,). and h 1N Cd,:_,.,) orbitals. The p level
also loses its degeneracy, appcarina as a2 (p<) and e,. (p,.. p,.). The four ligands, which
will be oriented along the x andy axes, will give rise to ligand group orbitals of a 1,,
and 1',. symmetry. They will interact with metal orbitals of the same symmetry
leading to the a MO dia&ram shown in Fis. 11 .22. Note that the " LGO overlaps with
both a 1, metal orbitals. producing three MOs of this symmetry. Several metal orbitals,
the a:!M. e,. and the b2tt, rema in nonbonding because they engage in no net overlap
with the ligand orbitals.
The square planar seometry is particularly common for complexes of d 1 metal
ions. For such a complex, there will be sixteen electrons. eight from the metal and
eisht more from the four ligands, to be assi&ned to the molecular orbitals in Fis. I 1.22.
These electrons wil occupy the e.ight lowest energy MOs and the complex will be
diamagnet.ic. The MO description provides a clear rationale for the observed stabilities
b,.,.
".,.- -,.- ---.
,' I
t,
"
"
t',
I
I
1
I
\
'./,. ... "'"
_,
...-r-:=-'
I
\\
1,1'\
-'1
.A I
ln+lll--'--{ II
\ A
., '
>---T, \
1\
I
I
11,
\\
\\I
I \
I \
I \
'
('"-4\-----
ttd
'
I\\
I
\
'
1)."'
"\
\\
\\I
I\
'
I
\
\
\\
'\
,"
"'""
,,
I
,"'
;
\._......""
\1
o
I_ _
- - ____/,
.,
4L (LGO.)
Fig. 11.21 A u MO dlaanom for a complex of telrahedrol symmetry.
4L (LOOol
Fig. 11.22 A u MO
diaaram b a
planar ML. complex co.. symmdr)l).
420
11 Cocwdinalion Chemistry: Bonding, Spectra, and Magnetism
of square
complexes: All or the bonding molecular orbitals are filled and all
antibonding orbitals remain unoccupied. Adding additional electrons would destabilize a complex because the electrons would occupy antibonding levels. Fewer
than sixteen electrons would also lead to lower stability, all other things being equal,
because the bonding interaction would be diminished .
It should be apparent from the molecular orbital diagrams in Figs. 11.20, 11.21,
and 11 .22 that there are strong resemblances between the molecular orbital and crystal
field descriptions for transition metal complexes. The energy levels that appear in the
central portion or each MO diagram match the splitting pattern derived for a crystal
field environment of the same symmetry . In the molecular orbital de.scription some of
these levels are antibonding. a concept that of course has no place in the crystal field
model. From our qualitative developme.nt here, i_t may appear that the two models are
quite similar. However, it is important to recognize that the common ground between
them is limited to the symmetry aspects of the bonding description. The two theories
differ fundamentally in how they describe the metal-ligand bond, with the MO view
being more realistic and leading to far better quantitative predictions of properties.
Pi Bonding and
Molecular Orbital
Theory
In addition to forming u bonds, many ligands are capable of a '" bonding interaction
with a metal. There are no disputes over which ligand orbitals have the correct
symmetry to participate in 'TT bonding, but as we shall see in later sections, the extent
to which this actually occurs for some ligands is vigorously debated . Even when ligand
and metal orbitals have the proper symmetry for '"bond formation, an energy or size
mismatch may lead to insignificant interaction.
Recall (Chapter 5) that a 'TT bond has a nodal surface that includes the bond axis
and that a '"bonding orbital will have lobes of opposite sign on each side of this nodal
surface. From the standpoint of orbital symmetry, an octahedral complex could have
up to twelve such
between the metal and each of the six ligands, although
this number is never realized in an actual complex. Metal and ligand orbitals participating in 'TT bonds will lie perpendicular to the internuclear axes. Consider four
potential metal-ligand'" interactions: (I) d..-p ... (2) d,.-d..,. (3) d,.-'TT. and (4) d,.-u
(Fig. 11 .23). Examples of ligands capable of each type are shown in Table J 1.11 . In
p rinciple. either the ligand or the metal can function as the electron donor. Filled metal
d orbitals can donate dectron density to an empty orbital on the ligand, or an empty d
orbital on the metal can receive electron density from a filled orbital of the ligand .
The ligand group orbitals capable of '"interactions in an octahedral complex faU
into four symmetry categories (Fis. 11.24): t 2N' ''"' 12,, and t 1,.. Of these, a transition
metal will possess orbitals of only two ofthe types : ':tt (d.cy dx; and d 1) and t 1" (Px
p and p,). Conceivably, the metal could use all of these orbitals for '" bonds.
However, the members of the
set are directed towards the ligands and therefore
participate in strong u bonds. Formation of'" bonds using these orbitals would tend to
'u
Mew
t.ipnd
(a)
Upnd
Mclot
(b)
Metal
l.lp>d
(C)
Meul
(dl
t.ialllld
fig. 11.23 Pi overlap of a metal J otbilal with various types o( ligand orbitals: (n) p, (b) J, (C) rr, and (d) u.
Molecvlar Orbital Theory
Table11.11
Pi boncl"ong in COO<doncrtiaft
compounds
l.lgancl ...,..,....
Type
p.,-<1..
d..,-rr
421
Ro-. Rs-. cY--. r-. cr.
Donation of dectrons from

ftlled p orbilals of ligand to
empty d orbitals of metal
Donation of electrons from
filled d orbitals of metal to
empty d orbitals of ligand
Oooation of electrons from
empty 1T antibonding
orbitals of ligand
Donation or electrons from
empty u orbitals of ligand
Br-. 1-. RzN-
R3P. R3 As, RzS

CO, RNC, pyridine. CW,
N2 , NOi'. ethylene
Bonds; Wiley: New
Nusent. W. A.; Ma)'CI', J. M. Mnul-Ligand

York, t988.
Some of these ligancb lit inlo more than one catqory. For exa"1'1e. 1- only has filled p Ottitals 10 donate electrons but also haa low-lying empty d
ortilals to accept electrons. R)P, aa shown. may accept ,.,. eleetron donalioo into
its empty d or P- R u orbitals; the u contribution is generally reprdcd as
more siJniflcant.
weaken the cr system and hence will not be favored . The tlH orbitals. on the other
hand, are directed between the ligands which, as we saw earlier. restricts them to a
nonbondfng status in a cr-only system (Fig. 11. 17b). They can, however, readily
'11'-bond to LGOs of matchins symmetry (Fig. 11.2.5). The t 211 and 1 111 ligand group
orbitals must remain nonbonding for the simple reason that there are no orbitals of
matching symmetry on the metal. Pi bondins in an octahedral complex is thus limited
to the orbitals of 1 26 symme.try.
One of the simplest cases of '" bonding in octahedral complexes is found in
(CoFJ'-. Its cr system will be similar to that in Frg. 11 .20. The ':to orbitals of the metal
can interact with t"!.tt LGOs constructed from the fluorine 2p orbitals to form 'ITbonding
and anti bonding molecular orbitals. Since lluorine is more electronegative than cobalt,
fig. 11.24 Identification of the symmetries of lipnd STOUP orbitals and metal orbitals
capable of participating in,.,. bonds (represented as vectors) in an octahedral ML., cornpleJt.
The characters and irreducible components of the reducible rcprescntalioo. r w were derived
by application of the Jatne methods used for the O'Oilly system (Fig. 11.18).
422
11 CoordinatiDC> O.emistry: Bortding, Spectra, and Magnetism
Fig. 11.25 Pi overlap o{ ' 4LGOs wi1h a metal 14- (J.,.)

ortilul. Tllere are lwo
acldi1ional se1s
perpendiCUlar 10 the
one shown.
the fluorine 2p orbitals lie at a lower energy than the corresponding metal 3d orbitals.
Under these circumstances. the bonding "' MOs will resemble the fluorine orbitals
more than the metal orbitals. and conversely the ., MOs will more closely resemble
the metal orbitals (see Chapter S). The molecular orbital energy diagram for the 1T
system in [CoF,J- is shown in Fia. 11.26. Since the 2p orbitals on the fluoride ligands
are filled, these electrons will fill the resultant molecular Ill "'orbi1als. The electrons
from the 3d (1211) orbitals oflhe cobalt are therefore in 1T antibonding orbitals ( .,) a1. a
higher energy than they would be if"' bonding had not taken place. Sin<:e the level of
the
orbitals is unaffected by the "'interaction. !J.,. is reduced as a result of the .,.
bonding. It is fdt that this is the source 0( the position 0( ftuoride (and other halides) at
the weak field extreme in the spectrochemical series (weaker than most a-only
ligands). In the same way. the wealcer field ofOH - compared to H1 0. so puuling in
terms of a purely electroSiatic model, can be rationalized in terms of the hydroxide ion
being a beuer ., donor . Note that the overall gain in bond energy as a result 0(
"' bonding is slight: The filled lllt orbitals are lowered in energy somewhat, but the
nearly filled ri., orbitals are rnised an equal amount. Thus the only net stabilizing
energy is that derived from the sliahlly different populations of the two sets of orbitals.
Finally, it should be mentioned that oxyanions of transition metals in high oxidation
states such as CrO!- . MnOi, and FeO!- probably contain appreciable 1T bonding. In
ligands can be treated as above, but
principle this ., bonding between metnl and
because 1he complexes are tetrahedrnl. the problem of 1T bonding is somewhat more
complex and will not be discussed here.
Lig-o1nds such as R,P may also participate in 1T bonding. In these molecules, as in
NH1 , the ligating ntom can a-bond to lhe metal through an approximately sf" hybrid
orbital. Unlike nitrogen. however. phollphorus has empty 3d nod a o rbitals lying low
enough in energy that they can receive eleclron densit y from the metal. These orbitals
e;
..
/'
\\
''
\
\
\
..
syslem of ICoF.t'- .
Left: MOs ror the tr system

of 1he complex: rillhl:
LGOs of 14- symmelry;
,---,
Ccmp..
Fig. 11.26 MO diagrnm for

I he 'IT
,,
,
----
___...
center: MOs after .,.

inler:w:1ion. Note 1hn1
diminished by lhe .,.
inleroction.
is
423
have fairly low electronegativities (compared to the metal orbitals). and so the 1'!>!
lOOs formed from them will lie at a higher enugy than the cornsponding metal
orbitals. The resulting energy level diagram is shown in Fig. 11.27. Although the 1'!>!
orbital of the complex is lowered and the 1;_. raised in a manner almost identical to that
of the previous case. the fact that the ligand r2, orbitals are empty allows the r;R
orbitals to rise with no ,ost of energy while the bonding t 2 _. orbitals are srabili<.rd. Pi
bonding of this type thus can stabilize a complex by increasing the bond energy. In
addition, the resulting 1'!>! -rr ocbital is detocalized over both metal and ligand as
opposed to being a nonbonding
orbital localized on the metal, which would have
been the case in the absence of.,. bonding. Electron density is thus removed from the
metal as a result of -rr bonding. This will not be particularly desirable in a complex
containing a metal in a high formal oxidation state since the metal will already carry a
partial positive charge.:!t>Jn low oxidation states, on the other hand. electron density
that tends to be built up via the u system can be dispersed through the rr system; that
is, a synergistic effect can cause the two systems to help each other. The more
electron density that the 'IT system can transfer from the metal to the ligand, the more
the metal is able to accept via the a system. In turn, the more electron density the u
system removes from the ligand. the more readily the ligand can accept electron
density through the .,. system. Up to a certain point, then, each syste.m can augment
the bonding possibilities of the other.
Pi bonding between metal and ligands provides a simple raison a lire for strong
field ligands, an issue that crystal field theory could not resOlve. If we examine the
strong field end of the spectroche.mical series (page 405), we find lig;lnds such as nitrite
ion, cyanide ion, carbon monoxide, phosphites, and phosphines. The IaUer two owe
their positions in the series to their ability to serve as '"acceptors. as described above,
which increases the value of 11,. relative to what it would be in a a-only system (Fig.
11.27). The other three ligands 'IT bond in a very similar fashion except that the
acceplor orbital is a .,. orbital as shown in Fig. 11 .23c. The net result is the same as for
ligands in which either d or u orbitals or both serve as 'IT acceptors: The bonding t 1,
level is lowered so that the quantity a, is increased. A molecular orbital diagram,
..
Fig. 11.27 MO dia:ram for

the 1T s}'lllcm of an
octuhedrul complu with
- - --,
I
I
I
-r-,
J;.
I:,
\ \ ____
_j_'
---- ..
o
- - - - - 1'..- - - - - ,
I
l
___.___
,I
acceptor lipnds such us

CO. PR,. or SR,. Note that
Ihe w intCt"".!Ciion in this
case inCreases A.,
A.
'
o Compte
,----
;,I
Ua>nd orbitals
"" In tcCCtlt years many complexes of elltly transition melals in rdotiw:ly hil!h oxidolion states have
been prejXlred which contain neutral phosplloru.< donor lipnds. Although the metal lllom moy prefer D hordCO' Lewi< base. in the absmcc of one,
loa pilo:<phinc ma y occur. Fryzuk. M. 0 .;
Halldcd. T. S.: Bers. 0 . J . Owrd. Chtm. Rev. t990, 99, 1}7-212.
424
11 Coordination Chemistry: Bonding, Spectto, and Magnetism
including '" inter.K:t ions. for an octahedral
complex is shown in Fig. 11.28.
The increase in 6 0 caused by '"bonding is substantial enoush in many cases that lhe
absorption maximum for the t 211-to-e; electronic transition is blue-shifted out of the
visible region into the ultraviolet portion or the electrollUlgnetic spectrum, with
the result that the complexes are colorless. This is the cnse for the metal carbonyls. for
example.
Halide ions such as Cl-, Br-. and 1- present a differenJ situation. Like the ,
fluoride ion, they have fiUed p orbitals, but unlike fluoride, their empty J orbitals may
participate in -rr bonding. It is difficult to predict which set of t 2., LGOs for these ions
(those constructed from filled p or from empty d orbitals) will interact more strongly
with thet 2., orbitals of the metal. Empirically, we observe that oil of the halide ions lie
at the weak-field end of the spectrochemical series, indicating that the p--orbital
interaction is more important than that of the d orbitals.
The potential for u* orbital.s to serve ns '" acceptors has become apparent in
recent times. Phosphines, instead of using empty pure d orbitals as -rr acceptors, may
accept '" donation into low-lying u* orbitals or into hybrids involving u and 3d
'
6CO
F;g. 11.28 MO dia.,..m for an octahedral M(COJ., cornpleJI ; both uund vintcractions are
included. Correlation lines are drawn only to those molecular Ofbi.lals to which the metal d
electrons COntribute.
Molecular Orbit al Theory
425
orbitals.n In addition. the coordination of dihydrogen (see Chapter IS) is thought to

involve u electron donat ion to the metal from the H-H u bond and back donation
from the metal into the Hl u orbitals.
Experimental
Evidence for
Pi Bonding
Few topics in coordination chemistry have received more attention than ., bonding.
We have seen in the preceding section that i1 provides n reasonable rationale for much
of the spectrochemical series. In Chapter 13 we shaU find that ., bonding is important
in determining pallems of Hgand sub5titution reactions. It is also central to under(Chapter 15). In this
standiiiB reactivity and stability in orgnnometullic
section various experimental methods of evaluating .,. bonding in metal carbonyl
complexes and their derivatives will be examined.
There is strong agreement amOfiB inorganic c hemists, theoreticians and expeO.
mentalists alike, that the stability of metal cnrbonyl complexes depends on the ability
of carbon monoxide to accept metal electron density into its .,. orbitals.28 Although
carbon monoxide is a weak base toward hydrogen ion or BH 3 , it has a significant
affinity for electron-rich metals (see Chapter 15). For example. it reacts with metallic
nickel at modest temperatures to form gaseous Ni(C0)4 This is especially impressive
when one considers that the metal-metal bonds in nickel. which must be broken for
the complex to fOrm, are quite strong. Observations such as these cannot be easily
explained by u bonding alone. The currently accepted bondina model views carbon
monoxide as a udonor (OC-+M) and a.,. acceptor (OC - M), with the two interactions synergistically mhancing each other to yield a strong bond:
(11. 16)
Crystallograplty. The M-CO bondif18 model descnbed above suggests that the
greater the extent of.,. bondin&. the more the C-0 bond will be lengthened and the
M-C bond shonened. The u interaction. on the other hand, should have the opposite
effect on the C-0 bond length because the lone pair on carbon that is utilized in
fonning the ubond is in a slightly antibondif18 MO of the carbon monoxide ligand (the
3u orbital in Fig. 5.20). Donation of this pair of electrons to a Lewis acid would be
expected to make the C-0 bond stronger and shorter relative to that of carbon
monoxide. It would seem from this analysis that one could merely compare the C-0
bond distance in carbon monoxide (11 2.8 pm) with that in a carbonyl complex and. if
for .,. bonding. A
the latter is found to be longer, this could be taken ns
problem arises with this approach because the C - 0 bond lenglh (and thai of multiple
bonds in general) is relatively insensitive to bond order: The differenc.e in length
between the triple bond in CO (113 pm) and typical C=O double bonds in organic
molecules (- 123 pm) is small. Moreover. observed C-0 bond lengths among metDJ
carbonyls fall within a very short range-about 114 to liS pm. Unless the measurement is made with exceptional accuracy, any bond length difference within this range
cnnnot be regarded as sl:ltistically significant. let alone as a meaningful indication of
bond order.
:n MeAuliiTe, C. A. In
CmwJination Cftmtisrry; Wilkinson. G.; Gillard. R. D.;
McO...cny. 1. A .. Eds.; Perpmon: O.tonl. 1987: Vol. 2. Muynick. D. S. J . Am. Chrm. Sue.
1984.
G<ecn, I. C.: Klllctoyanris, N.; Su. K. H.: MaeOcnald. 114. A. J . CHin. Sue.
Dolton TrOM. 199t. 2371-2371. Also sec Ol;apter 18.
,. Sherwood. D. E.. lt.; HaU. M. 8 . /norg. Chtm. t910./9,
Burscen. 8. E.: Frci<s, D. G.:
Fenskt. R. F. /mxs:. C/wm. 1980, 19. 1110-1811. Bauldtlic:hc:r. C. W Jr.; Ba&us, P. S. J. CJwm,
Plrys. 19114.
Bt, SSS9-S8911.
426
11 Coordination Chemistry: Bonding, Spectn:o, and Magnetism
The mclnl-carbon bond length in c:utonyl complexes provides a beuer measure

or double bond charac.tcr because these lencths are more sensitive to cha11ges in bond
order. U the covalent radii of an sp carbon atom and or the metal atom 10 which it is
bound are known, summation of the two should give the lenlll.h expecled for a metalcarbonyl single bond. lhat is, one with no .,. bonding. This value could then be
compared with the measured bond length to determine the extent of .,. bonding
present. A factor that can cause problems with this strategy is that the covalent rndius
of the metal atom may not be known with certainty. However, this difficulty can be
circumvented by choosing a complex that conlllins both carbonyl and alkyl ligands. In
such a complex the covalent radius of the metal atom will be the same for both ligands
in the absence of.,. bond ina, and can be derived from the measured M-C (alkyl) bond
length and the known covalent rod ius for an sp1 carbon . This value can in turn be used
10 calculate an expected metal-carbonyl single bond lenath. The methyl derivative of a
rhenium carbonyl complex, Re<CH,)(CO)s, may be used to illustrate the procedure:l!l
Re-C single bond lenath in ReCH,

231 pm
-(Covalent radius ror s,il C)
pm
Covalent radius for Re
Covalent radius for Re
+(Covalent radius for sp C)
Re-C single bond lenath for ReCO
154 pm
154 pm
+ 70 pm
2l4pm
The experime.ntally determined Re- CO bond distance for this complex is 20().4 :!:
0.4 pm, about 24 pm shorter than that predicted for au-only bond. When this type of
analysis is applied to other complexes, similar decreases in metal-carbon lengths are
observed. subslllntiatinsthe view that theM- CO bond has considerable double bond
character.
Further crystallographic evidence for metal-carbonyl.,. bonding is found in phosphine and phosphite derivatives of hexacarbonylchromium . Substitution of R,P for
CO in
creates a complex of C4 , symmetry in which one CO group lies trans to
the phosphorus ligand (Fis. 11.29). The two trans ligands will compete for the same .,.
orbital, but carbon monoxide is a beuer ,. acid (11' acceptor) than the phosphine
(Fig. 11.30). As a result, the Cr-CO.,, bond should be shorter relative to Cr-C0,.1
and to Cr-CO in Cr<CO),.. The data in Table 11.12 show that these predictions are
borne out. in keeping with the substantial ,. character in the metal-carbonyl bond.
In general, the .... accepting ability of a phosphine increases as the electroncgativities of its substituents increase. Thus we would expect the .,. acidity of
ng. 11.29 Structure of lhe
ptlosphine and phOsphite

derivatives of
helUICW'bonylchromium.
""Rankin. 0. W. H.: Roberoon, A. J. OrfOI'OIMI. Ottm. l n6, IUS, lll -140.
Molecvlar Orbital Theory
427
(b)
(I)
Fig. 11.30 Competition by ligands for the.,. bonding d orbihll of a central metal atom.
Relative overtup is symbolized by the shaded areas. (a) Equal nnd strong 1T bonds resulting
from equal and &00<1 overlap of the two carbon monoxide 11 orbitals with the metol d orbitAl.
1r orbital with pOlarized melal d orbital compared
to poorer overlap between lipnd d and metal J orbitals. Polarization (mixing of higher energy
wave functions) occurs so as 10 maximize total OverlAp. Recall that the overlap integral
includes both spatial and intensive properties: the rcpresenllltion above i.s a graphic
simplitlcation.
(b) Superior overlap of carbon monoxide
P(OPh)J to be greate r than that of PP1t1 . Consistent with this view. it is found that the
Cr-P bond le.n gth in the phosphite eomplex is shorter than in the phosphine eomplex.
The carbonyl ligand trans to the phosphorus ligand would be expected to receive more
1T elect ron density in the phosphine complex than in the phosphite complex. which
would lead to a shorter metal-carbon bond for the phosphine derivative. and that is
observed as well.
The P(CH 2CH 2CN)1 ligand appears to be inconsistent w ith the model; however.
its Cr-P bond distance suggests that it is a poorer 11 bonding ligand than P(0Ph)3 ,
whereas the Cr- C bond lengths suggest that it is a better 1T acceptor. Some of the
ambiguity may arise because of the different s teric requirements of the phosphorus
ligands. Steric interaction with equatorial carbonyl ligands could lead to a Cr- P bond
lengthening which obscures the intrinsic electronic effect.JO It should be apparent from
this discussion that it is often not a simple matter to sort out u and 11 contributions to
Tobie 11.12
Bond lengths (pm) in
chromium carbanyl
0
complexes, Cr(C0Jsl
co
P(0Ph)1
P(CH2CH2 CN),
PPh,
Ci- P
Ci-C
(trans toP)
Ci- C
(trans to CO)
C- 0
(tram to P)
C-0
(tr... to CO)
230.9(1)
236.4( 1)
242.2(1)
186. 1(4)
187.6(4)
184.4(4)
191.S(2)
189.6(4)
189.1 (4)
188.0(4)
113.6(6)
113.6(4)
114.0(2) av
113.1(6) av
113.8(4) nv
av
av
av
av
av
Recs, 8 .; Mitschler, A . J. Am. Clrnn. Soc. 1976, 98, 7918-7924 (chromium

Plastos, H. J .; Stewart, J. M.; Grim, S. 0 . I . Am. Clwm. Soc. 1969, 91,4326--1327 (triphenylphosphine and
complexes). Cotton, F. A.;
D. J.; Jblcy, w. H.
IMrt. CJwm. tnt, 10. S78-S83, (lris(2_:Cyanoclhyl)llllosphlne
anaJes of phosphines are disCU$SCCI in Chapler IS. The cone angles of P!OPh)J,
P!CH 1CHzCN)J, and l'ftl1 are I:W, or, and 14s. respectively.
JO Cone
428
11 Coordi11ation Chemistry: l oading, Speclra, and Magnetism
Table 11.13
Infrared absarptions ol metal carbottyt .....,.._
Compound
(em-)
(Mn(CO)J+
(Cr(CO>t,)
(V(CO>.J(Ti(C0)J2(Ni(CO)J
(Co(C0)4 ) (Fe(CO)J1-
2090
2000
1860
1748
2060
1890
1790
metal-carbonyl bonds from suuctural data because other factors C.'ln influence bond
lengths.
Irifrared spectroscopy. The most widely used experimental method for analyzing metal carbonyl complexes is infrared (IR) spectroscopy. The frequency of the
absorption (or more properly , the force constant, k) nssociated with a C- 0 stretching
vibration is a measure of the resistance of the bond to displacement of its atoms.
Hence the stretching frequency provides a qualitative measure of bond strength, with
stronger bonds in general giving
to JR absorptions at higher frcquenc:ies. Consider
Table 11. 13, which lists IR data for two isoelectronic series of metal carbonyls. On the
basis of the absorption maxima. we can say that the C- Obond strengths in these two
series decrease in the order [Mn(CO)J+ > (Cr(CO>J > [V(CO)J- > [Ti(CO>cf- and
(Ni(CO)J > [Co(CO)J- > [Fe(C0)4)2 - . These qualitative results are consistent with
the ..--bonding model described eal1ier: As M- C., bond ina increases, the C-0 bond
becomes weaker. The greater the positive charge on the central metal atom. the less
readily the metal can donate electron density into the ., orbitals of the carbon
monoxide ligands to weaken the C-0 bond. In contrast. in the carbonylale anions
the metal has a greater electron density to be dispersed. with the result that M-C
'IT bonding is enhanced and the
bond is diminished in strength.
Tile usefulness of the C- 0 stretching frequency as a measure or C-0 bond
strength (and hence of the extent of metal-carbonyl ., bondina) derives from the
sensitivity of this absorption to the electron population of the CO antibonding orbitals.
In the isolated carbon monoltide liaand, t.h e lone electron pair on carbon resides in the
3u orbital, which is the HOMO (highest occupied molecular orbital) for this molecule
(Fig. S.20). Promotion of one of these electrons in gaseous CO to a ., level to give the
3&12.,1 eltcited state causes the C- 0 stretching frequency to drop from 2 143 to 1489
em -. This dramatic change is a strona indication that even a small amount of electron
shift from a central metal into the ., orbital of a bound CO can be easily detected via
IR measurements.'
As has already been stated, the lone pair on carbon in the carbon monoxide ligand
resides in a molecular orbital that is slightly antibonding. Support for this assertion is
also provided by IR data . When one of the lone pair (HOMO) electrons is removed
from
to form
the
stretchina frequency increases from 2143 to 2 184
em- 1 showing that the C-0 bond order also Increases. Protonation or the molecule,
which can be considered as u coordination of CO to H+. also leads to an increase in
the stretching frequency. It would be expected that , upon donation of the CO lone pair
to a metal atom. a similar increase in "co should occur. provided there is no other
concomitant electron shift. Whal is actually observed, however. is that "co almost
always decreases upon complelt formation. an indication that ., electron density
flowing from the metal into the ., orbital of the ligand more than compensates ror the
increase in C-0 bond order I hat would accrue from the ligand-to-metal u donation.ll
In a preceding section we saw crystnlloaraphic evidence that subs titution of
phosphorus ligands for carbon monoxide in
lends to a strengtheningofCr-C
bonds, particularly those trans to the phosphorus aroups. nnd this was interpreted in
c- o
co
co+.
c-o
Jl Johnson. J. 8. ; Klempcnr. W. Ci. J. Am . CMm. Soc.
tm . 99. 7132-7131.
n Exceptions ate OAuCO. (or which Yeo - 21llcm- 1COd' Amico. 0 . 8 .: Caldcr.uzo. F.: Odi"Amico. Ci. Cuu. Chim. ltnl. 1m. 107. IO C- tel31 and Ati(:O(BcOTeF,).t. for whicb "co - 2204 .,.,.-
(HurbJrt. P. K.: AndEnon. 0 . P.; Stf3USS. S. H. J. Am. CMm. S. t991. /IJ, 6Z77-62781. An
e"""'pCe inwlvirc a main-crouP mdal is Me,AJCQ. ror which "CC - 2t8l
R.;
Arrii181Cl0'1, C.: ArrintJtcn. C. A.. Jr. J . Am. CMm. S. ,,.,, Ill.
Mole eulor Orbital
n...,..y
429
terms of competition of the ligands for available 1Teleclron density. Changes in the CO
infrared absorptions also occur and can be evaluated in the same vein. In genetal,
substitution of CO with a ligand L will alter the CO stretching frequencies of the
remaining carbonyl ligands in a manner that reflects the net electron density transmitted by L to the central metal atom. This in tum will depend both on the u-donating
capacity and the 1T acidity of L.
II is instructive to look at a set of W(CO>,L complexes to see how a variety of
ligands (L) perturb the C-0 stretching freque.nc.ies. These complexes all have
symmetry, at least ideally. and give rise to three allowed IR absorptions (two nondegenerate and one doubly dege.nerate). having the symmetry labels
and E.
In Chapter IS the procedure for obtaining symmetry as.signments for vibrational
modes from the appropriate character table will be illustrated. but for now we will
simply use the results (Table 11. 14). The particular vibrational stretching modes
involved are shown in F'tg. I 1.31. The important one to focus on is
wbich
corresponds to the symmetrical stretching motion of the CO group lying opposite the
ligand L. It is this CO that competes most directly with L for available 1T electron
density and therefore is in a position to best reflect the .,. acidity of L.
For ligands in Table I 1.14 having little or no ?Tacidity (e.g . those in which oxygen
or nitrogen is the donor atom), the CO in a trans position can absorb significant
electron density into its antibonding orbital, and relatively low C-0 stretching
frequencies are observed. In the case of the phosphorus ligands. the .,. acidity inc reases as the electronegativity of any substitutuent on P increases. As these ligands
become more and more competitive for .,. electrons, CO receives less and less .,.
electron density and the C-0 stretching frequency increases accordingly. The very
high C-0 stretching frequency of the PF3 complex indicates that this ligand is
comparable in its .,. acidity to carbon monoxide itse.Jf. Groups in Table 11.4 having
carbon as the ligating atom. which will be discussed in Chapter rs. are quite effective
.,. acceptors. as shown by the relatively high
stretching frequencies of their
complexes.
Although IR frequencies provide a useful measure of the extent of 7T bonding in
carbonyl complexes, a better quantitative picture can be obtained from C-0 force
constants. These values are commonly derived from IR data by means of the CottonKraihanzel force-field techniqur..H This procedure makes certain simplifying assumptions in order to provide a practical solution to a problem that would be extremely
difficult to sOlve rigorously. Among the important assumptions are that the C- 0
vibrations are not coupled to any other vibrational modes of the molecule and that the
observed frequencies can be used without correction for anharmonic effects. The
results of force constant calculations of this type provide a means of setting up a .,.
acceptor series:34
"Colton. F. A .; Kraillaru.el, C . S . J . Am. Chem. Sot. t962, 84, 4432-4438. See also Collon, F. A.:
Wilkinson, G. AdvDnud lnorgank ChmiJtry, Sth ed.; Wiley: New York. 1988; pp IOJ8-.t040;
Timney. J. A. lnorg. Clwm. 1979. 18, 2Sbl-2S06.
l4 There is no1 universal agreemmt on theorderinsofthis
series beawse many of the ligands ha.., ,..

accepting ICOOencies wtUch are .,jrtuaJly
Arsenic and ariil!l()fly cornpounds fall
into the
the ccxrespondins
AkholJI!h there is some uncer
tainty as to wllether these compounds are sli&hlly beller or slitlhlly poorer
than their
pho$phorus analoii'JtS, the accepting ability is scnc.rally believed to be in the order P > AI;> Sb. In
the abo\le series R can represent phenyl or alkyl aroups with the phenyllipnds ll$UUIJy exhibilill&
better acceptor ability.
430
11 CaOI'dination Chemistry: Bonding, Spectra, and Magnetism
T"'*11.14
Infrared corbafty! stmching
Jr.qUMKies (cm- 1 ) lat"Same
W(CO)sl complexes
Rehrence
1847
1.847
1908
1917
1920
1931
2067
2067
2074
HzS
1916
1930
1932
1935
1943
1937
2076
2074
2071
CyNH24
pyridine
1894
1895
1916
1931
1929
1933
1929
1948
2071
2076
2071
2083
1921
1947
1947
1947
1942
' 1946
1959
1965
1981
1991
1990
1953
1937
1938
1940 .
1939
1940
1945
1958
1979
1982
1984
1983
Me_co
aniline
CH,CN
H;P -
"
Ph,P
(MeS),P
(EtO),P
(Ph0)1 P
11 P Br,P
CI,P
F,P
2007
CzH2
C(OEr)Me
-<;11----
19S2
1958
1973 _
1967
194S
1953 _
..
"
t
2083 2070
2071
2072
2072
2062
2078
2083
r
f
f
2087
It
2093
2095
2103
It
2095
2072
2088 -
" A variety of solvems were used in these Sllldies and because

frequency vallles are acneraUy solvent dq)endent, smal
dilrer<nees allould not be taken as sigMicant. The fomdclen 8
mode, rrequenlly
these spcara as a weak absorptioo.
has been omiued.
Slolz. I. W.; Dobson. G . R.: Sbeline. R. K. lno.g. Clt<m.
1963. 1, )2)- }26.
It
Heobestlold. M.; Suss, G. J. Chtm.
(M) 1977. 2120.
4 Cy cyclollex)'l.
Knihanzel. C. S.; Couon. F. A. lnorg. Chtm. 1963. 1,
sn-540.
r Bancroft. M.; f:lian4rd-8ailey. L.;

Chtm. 1986. 1S. 3675-3680.
R. J . lnort.
" Kdler, R. L.; Vetlcade, J. G. lnorg. Chtnr. 1969. 8. 1..-'- '
! "'"'t
Fi&c:hU, E. 0.; Knauss. L.
., -- , ., ,
B...... l96,. IOZ. 223-229.
Molecuh>r Orbital Theory
L"" I/ L/ T/
"""I /I /I /I
- M-+-+
- - M- -
A Ill
I
431
Mg. 11.31 Vibrational

suetching rnocles and their
symmetries for M(CO),L
Complexes.
Al2J
I
NO > CO. RNC, PF1 > PCI1 , c;H P(0Ph)3 > P(0 Et)3 >
C(OR)R > C2 H2 > P(SR)1 > PPh3 > PR1 > R2S > Ph1 >
RCN > aniline > alkyl amines > ethers > alcohols
This series shows many of the trends that might have been expected on the basis
of dectronegativity, especially for the phosphorus-bearing ligands: PF3 > PCl3 >
P(0R)3 > PR3 The similarity of phosphites and phosphines is more than might have
been predicted from electronegativity arguments indicating that there may be significant Q-P 'IT bonding in the phosphites and competition for the phosphorus d orbitals. Alkyl amines, ethers. and alcohols have no empty low-lying orbitals and hence
form the weak end of the 1r-acceptor scale.
Care must be taken in applying a 1r-acidity scale such as the one just presented. In
using it to interpret IR data for carbonyl complexes , one should keep in mind that
factors other than inherent ligand 7T acidity can also influence "co values. Given that
u bonding is much more important than 7T bonding in these systems, differences in
u-donating capacity among ligands may outweigh trends in .,._accepting ability. For
example, replacing the phenyl groups on phosphorus with methyl groups has lillie
effect upon the carbonyl stretching frequencies of W(PR3)(CO), complexes even
though the ....acidity series would predict that this substitution should cause an
increase in "co II is possible that the expected increase is not observed because, in
addition to being a beuer 1racid. Ph3 Pis a beller udonor compared to Me3 P,JS making
the total amount of electron density that is available on the metal greater in the Ph3 P
complex. It is also possible that the change in ligand substituents introduces a steric
perturbation that is substantial enough to have a greater effect than electronic factors
(see Chapter IS).
speclroscopy. Photoelectron spectroscopy {see Chapter S) has
been used to obtain metal-carbon stretching frequencies for Group VI 8 (6) carbonyl
complexes.M>.l7 The full spectrum for CrtC0)6 is shown in Fig. 11.32. The signal
labeled 8 1 corresponds to the ioni.zation of an electron from a
orbital, which of
course is the orbital having appropriate symmetry to interact with the 1r orbital of
carbon monoxide. If in fact this interaction exists, removal of the electron should
weaken the metal-carbon bond and decrease its stretching frequency. If. on the other
hand. there is no interaction. one would expect to see little change in "Me upon
ionization since the electron would be coming from a non bonding orbital. When t he 8 1
" Pholoctcctron speclr3 have been interpreted in terms of Ph)P bei111 a better aclonor than Me1P; see
Bw>crolt M.; Dil!nard-&itey. L.; PucldephAn. R . J . ltttHII. Chrm. 1986. 1J. 367S-3680. For a
di"'ussion of phosphine lmsicily, see Anacli<:i. R. J .; Bush. R. C. lnor11. Cl!'"m. 1988.17.681-686:
Sowa. Jr.. J . R.; Anaclici. R . J. lnorg. Otrm. 1991. JO. lSJ4-3SJ7. For recent attempts at sepetati.,.
a and effects, see RAhmAn. M. M.; HCJ11. Y. L.; Prock. A. :
W. P. OrKunumrtulllcs 1987,
6. 6SG-6S8; Wang, S . P.; Richmond, M. G.; Schwnru, M. J. Am. Chrm. Soc. tm . 114, 7S9S-7S96.
,. Hubbatd, J . L. ; Lichtenbo-au. 0 . L. J . Am. Chrm. So.. Ifill. 104, 2132-2138.

Foronother .;ew. see Hu. Y.-F.: Bancron. G. M.: Bozdt,J. R.; U u. Z.;Suthertand. 0 . G. J .; Tun.
K . H. J. Chrm. Sor. Chrm. Commun. 1992. 1276-1778.
:17
432
11 COO<dinotion Chemistry: Bonding, Spectra, ond Magnetism
Fig. 11.32 He( I) ultra.;olet photoelectron spectrum oC CrtCOl.. Peak positions correspond
to relalive enef!ies of molerular orbitals in the COOlplex. (From Higginson, B. R.; Uoyd. D.
R.; Burroughs, P.; Gibson. 0. M.; Orchard, A. F. J. Chrm. S<X'., FOI'uJay Trans.11973. 69.
1659-1668. Used with permission.)
band in the photoelectron spectrum is examined under very high resolution and its first
derivative is taken (Fig. 11.33), one observes a vibrational progression that has
frequency spacings corresponding to M-C stretching. The vibrational line structure
results because the (Cr(CO)J+ ions that form may be in a vibrational ground state or
in one or several vibrational excited states (Fig. 11.34). The value of "MC for
(Cr(CO)J+ obtained from the fine structure is 325 em -I. compared to 379 em- 1 for the
neutral molecule. the reduction being consistent with involvement of the tlR electron
Ionization enc1iY leV)
8.3
8.5
Fig. 11.33 Expanded view
oC the peak labeled 8 1 in
8.t
the PES spectrum shown in

fig. 11.32 along with its
first derivative. (From
Hubbard. J . L.;
Lichtenberaer. D. L. J .
Jim. Chrm. Soc. 1981. 104.
with permission.)
13.0
12.8
Elcctroo kindic
'1Y (cV}
t3.2
Electronic Spectra of Complexes
433
Fig. 11.34 Potential well

representations for MCCO>..
and MCCO):. showing origin
of vibrational fine structure
in PES spectrum. [Modifocd
from Hubbard. J. L .;
Lid!tenberscr. 0 . L . J .
Am.
Snc. 1982, UU.
2132-2138. Used with
pcrrni.ssion.)
Jnscmudeu distanCe
in ., bonding. It is estimated that this frequency shift corresponds to a 14-pm increase

in the M-C bond length upon ionization. Further support that such a struCtural
change occurs is provided by intensity data in the spectrum. If the most intense
tronsition that is observed is to the ground vibrntional state, it is an indication that
there is little alteration of structure when ionization occurs (by the Franck-Condon
principle). However. if the most intense transition involves a vibrational excited state,
it can be concluded that a substantial perturbation in geometry has taken place in
going from the neutral molecule to its positive ion. In the case of Crt CO),... the latter
was observed, substantiating the conclusion drawn from the frequency shifl. namely.
that the t2R orbital is a 1r-bonding orbital.
Electronic Spectra
of Camplexes38
The variety of colors among transition metal complexes has long fascinated the
observer. For example, aqueous solutions of octahedral [Co<H 20>J2+ are pink but
those of tetrahedral [CoCI.J2 - are blue. The green color of aqueous [Ni(H20)J2 +
turns blue when ammonia is added to the solution to give [Ni(NH3)J2+ . The reduction
of violet (Cr(H 20l,..Jl+ gives bright blue [Cr(H 20>t.f+. As with all colors. these arise
from electronic transitions between levels whose spacings correspond to the wavelengths available in visible light. (Of course, when a photon of visible light is absorbed ,
it is irs comple.mentary color that we actually see.) In complexes. these trnnsitions are
frequently referred to as d-d transitions because they involve the mOlecular orbitals
that are mainly metal din character (thee11 and 1211 ore and 12 orbitals in octahedral and
tetrahedral complexes, respectively). Obviously, the colors pr-oduced are intimately
related to the magnitude of the spacing between these levels. Since this spacing
depends on factors such as the geometry of the complex, the nature of the ligands
presem, and the oxidation state of the central metal atom, electronic spectrn of
complexes can provide valuable information related to bonding and structure.
,. Lever. A. B. P. lnnriiUnk Elutronic Stxttroscopy , 2nd cd .; Elcvia-: New Vorl<. 19ll6. Figgis,
B. N . In Comprehtll4iVt Coordination Chtmi.<lry; Wilkinson. G.; Gillard, R. 0 . ; McCieveny, J. A.,
Ed$.; Pcrxomon: Oxford, 1987; Vol. 2, Chopter 6. Figgis, B. N . lntroJucllnn to
Wiley: New Vorl<. 1966.
Firlds; John
434
11 Coordinofton Chemistry: londi.,g, Spectra, and Mognetim
Thus far in this chapter we have seen electronic spectra of four complexes:
(Fig. 11 .8), and
[Cr(ox>,r - . and (CrFJ,_ (Fig. 11. 13).
Casual inspection of these examples reveals thntthe number of absorptions varies. At
the heart of the interpretation of electronic spectra is the question of how many
absorptions are expected for a given complex. Answering this question requires an
accurate energy level diagram for the complex of interest as well as familiarity with the
selection rules governing electronic transitions.
The energy level diagrams that hove been presented thus for for transition metal
complexes are based on the so-called one-electron model even if the central metal ion
has more than one d electron. In other words , the effects of electron-e.lectron repul
sions have been ignored. Because these repulsions will make a significant contribution
to electron e.nergies in any c.omplex that has more than one d electron or more than
one d-level vacancy. they must be taken into account in interpreting spectra. The
approach that is usually followed in developin& an ene.rgy level diagram for a complex
is to begin with the d" configuration of the free ion and then to add, in tum, I he effects
of interelectronic repulsions and the effects of surrounding ligands. Our discussion will
be mainly qualitative and will use the concept of fields produced by ligands. as
introduced in the treatment of crystal field theory (page 394). However, from here on
we will use ligand
terminology to emphasize that the discussion applies quite
broadly to bondinc models that ranae from the pure crystal field theory through the
qualitative molecular orbilal approach described in the foregoing sect ion of this
chapter (page 413).
As we saw in Chapter 2, electron-electron repulsions cause a given eleCtron
configuration to be split into terms. However. for the simplest case, d 1 Ihere wiU be
no such spliuina of the free ion levels because there is only one electron. Thus we
have only one term, the ground state :o. because the lived orbitals are degenerate and
the electron has an equal probability of being in any one of them. As we have also seen
previously, these live d orbitals will. under the influence of an octahedral field (either
weak or stron&). be split into 12,: and i!" orbitals. The 20 term likewise will be split into
2
T2t< and 2 , terms in an octahedral complex.
For the d 2 conliguration, electron-electron interactions come into play, giving rise
to not only a ground state free-ion term
but a number of excited state terms
1G. 1D. and 1Sl as weJI .JY Now we must be concerned with how each of these terms is
affected by the licand field. If the separation between terms is large compared to the
we have the wt:ak field case. If. on the other
perturbation produced by the
hand. the ligand liekl splittina is large in comparison to the energy dilferenc.e between
terms. we have the strong field condition. Figure 11 .3S shows the free ion terms of a d2
conlicuration and how they 11re split in the presence of a weak octahedral liekl (left
side of the diagram). The right side of lhe diovam shows the effects of a strong
octahedral field. The lines connectina the weak and strong field extremes allow one to
estimate rhe relative eneraies orsrutes resulting from intermediate fields. Construction
or the suong field side or a correlation diagram such as this one for d1 is beyond the
scope of this text, but development of the weak field portion is more easily
accomplished .
The wave functions for S. P. 0 , F. etc. terms have the same symmetry as the
wave functions for the corresponding sets of s. p. d, /. etc. orbitals. This means that a
D term is split by an octahedral field in exactly the same manner as a set of d orbitals
eFl
J9 The excited stare
may bt obtained by mcrhocls
eP.
in AppendiJI C.
,.,
(b)
(<)
ldl
435
1<1
Fig. 11.35 Correlation diagrnm for

iun in ;lJI octahedrnllield. (at Free ion tums;
(b) weak field lenn<; (CI
field ground and exci1ed cooligurntions; (d) Slrong tleld
(e) intennediate field region. The numbers in parentheses indicote how many rnkrostotes are
as>eiated wilh euch lenn
!From Lever. A. 8 . P. /nnrxunir
SP<'<"trf<<mpy. 2nd
Elsevier: New York. 19116; p 112. Used with permission.I
and that the splilliOG for an F term is the same as that for a set off orbitals. and so on.
Transformations for terms S through I in an octahedral field are given in Table II. IS .
The orbital degeneracies associated with the terms A. . T. D. and F arc 1. 2. 3. S. and
7. respectively. Note that the sum ofthe degeneracies ofthe individual compone.nts in
an octahedral field is equal to that of the original term; in other words. overall
degeneracy is conserved. The spin multiplicity or each component will be the same as
that of its parent 1erm
the spin state of an electron is unaffected by the
symmetry of an external field . Thus the ground state 'F tenn for a d 2 configuration will
be split into three terms in an octahedral field; a 'T,,. a 'Tlsi and a l A:!N consistent
with the three levels shown in Fig. 11.35.
The energies of terms in a ':"eak octahedral field will be such that the average
energy. or the barycenter. is equal to that of the originating free-ion term in a spherical
field. Energy diagrams for the ground-state terms aSS4lciated with d 1 and d 2 configura-
436
11 Coordination Otemiotry: Bonding, Spectra, ..,d MagMtism
TaWe 11 .15
Split!ing of rf' lenni in an
octahedral field
Components in an octahedral field
Tenn
----:A,.,
---+T,II
---+Ell+ Tb
---+
Ab +Tilt+ Tb
---+
A 111
---+ E11 +
---+
+ E11 + T111 + Tb
T111 + T16 + Tb
A 111 + Ab + E., + T1., + Tl.< + Tb
tions are shown in

11.36. A tf9 metal ion has an electron vacancy or "hole" in its d
level and thus can be regarded as the inverse of a d 1 arrangement. These two
configurations also have ideotic:al ground state free ion terms. 10 which will be split by
an octahedral tidd into the same two levels (1Tl.< and 2E11). However, the energy order
for the two levels in a tf9 metal will be just the
of what is shown in
11.36 for the d 1 case. This hole formalism applies 10 all other d'' coofigurations as
well: d 1 and d 1 , d 1 and d 7 , etc. have identical ground state terms but octahedral field
splittings that are the inverse of each other.
An inverse relationship also exists between fields of octahedral and tetrahedral
symmetries. We saw earlier in this chapter that crystal fields of these two symmetries
produce inverse splitting pauerns for onc-dectron d orbitals. This relationship also
holds when electron-elec1ron repulsions arc added to the picture; any free-ion term
will be split into the same new terms (except for g and u designations, which are
Inappropriate for tetrahedral complexes) by tetrahedral and octahedral fields, but the
energy ordering will be opposite for the two symmetries.
Correlation diagrams for d1 to d' octahedral and te,t rahedral complexes are shown
in Fig. I 1.37. By taking advantage of the hole formalism and lhe octahcdrallelrnhcdrnl inversion, all seven configurations in both aeometries can be represented
with just four diagrams. In each diagram (except the one ford'). free ion t erms are
shown in the center, with the d" octahedral and d 111- " tetrahedral spliuings on the
right and the d 10-" octahedral and d" tetrahedral spliuings on the left. Field strength
increases in both directions ou tward from the center. Only lower energy terms arc
Ill
40
I.-'
'
Fig. 11.36
/ II ""} .
I
l.lb
D.64
r,,
(b)
by an octahedral field of 1he aroundSlale terms
(bl J 1 electron conligur3tions.
(a) J 1 and
Eleeh'onlc S,.eclra of Campi
437
(o)
lcl
Fig. 11.37 COCTelalion diaarams ford" and JtO- ions in octahedral anclretrahcdral lields: (a) d 2 und .t'. !bl d' and d' .
(cl d" and J". (d).!. For (a-c). rree ion terms arc in !he cenrer. wirh lield srrenarh incn:asiiiJ in bolh directions. At the
two extremes are slron& field configurations for ocrahcdral J'<>- and 1e1rahednl J" compexcs (lefll and octahedral J"
and tetrahedral J 10- complexes tri&hll. (From Figis. B. N. In
Coordination Chtmisrry; Wilkinson. G.:
Gillard, R. 0 .: McCicveny, J. A. Eds.;
OxfO<d. 1987; Vol. I. Ctwprer6, pp 136-237. Oiled with pcnnission.J
or
the diaarams is that as the ma&nirude of

included. A feature that is common to al
the ligand field increases, a number or energy level crossovers occur. A aeneral rule
that governs all such crossovers is thai they always invOlve states of different symmetry and spin multiplicity: Levels of identical designation never cross . For some
conliauracions
d'. d 6 , and d 7) the crossovers lead to a change in the ground state.
Ford', for example, the lowest energy term for the free ion is a 6 s. which splits in a
weak octahedral field co give 6A 1" as the ground state. AI an intermediate field.
2
however. the T2Jt state drops to lower energy than 6
ljnd becomes the sround state.
The ch3n8e in spin multiplicity from six to two here corresponds to a decrease in the
number of unpaired electrons from live to one; there is a transition from high co low
spin. In contrast. the ground states or octahedral cJ2 d 3 d. and d 10 complexes remain
the same under all field st.rengths. For example. the ground term of a [Tilt,IH (d2)
complex is 3 T111 at aD values or 6.,, which means that all such complexes will have two
unpaired electrons reprdless o r lhe nature or the ligand L . All of lhis is consisre.n t, of
course. with the bonding models that have been previously discussed in rhis chapter.
In order to use the correlation diagr.lms shown in
11.37 or simplifications of
them, it is necessary to know the ulution rules that aovem electronic transitions.
A'"
rrg.
438
11 Coordination O.emistry: Bonding. Spectra, and Mognelis"'
Selection rules reflect 1he rest ncuons on state changes available to an atom o r
molecule . Any transition in violation or a selection rule is said to be " forbidden." but
as we shall see, some lr.lnsitions are "more rorbillden than ot hers" (to paraphrase
George Orwdt'O). We shall not pursue the lheoretical bases or the rules in any delllil
but merely outline simple tests for lheir application .
The first selection rule. known as the Laporte rule. states that/he only allowed
transitions are those with a clrangt ofparity: gerade to unserade (g - tt) and ungerade
10 gerade (11 -. g) are allowed, but not I/-+ 11 and 11- 11. Since all d orbitals have
gerade symmetry in centrosymmetric molecules . this means that a ll d-d transitions in
octahedral complexes are formaUy rorbidden . This beina true, it may seem strange
that UV/ visible spectroscopy ror such complexes is even possible. In f'act, optical
spectroscopy is not only possible but has been an important source of experimental
support for current bondina theories for complexes. The key element here is that there
are various mechanisms by which selection rules can be relaxed so that transitions can
occur. even if only at low intensities. For example. unsymmetrical vibrations of an
octahedral complex can temporarily destroy its center of symmet ry and allow transitions that would otherwise be Laporte forbidden. Such vibronic (vibrationalelectronic) transitions will be observable. thou&h weak (the number of molecules in an
unsymmetrical conformation at any instant will be a small fraction or the total).
Typically. molar absorptivities for ociAhedral complexes are in the range or 1 to
102 L mor 1 em - . In
this means that if you made up a 0. 10 M solution
of a typical ML, complex and obtained its UV/visible speclrum, the d-d absorptions
probably would be observable . On the other hand, a 0. 10 M solution or a substance
such us benzene. which has fully allowed transitions, would yield absorption peaks
that woukl be arossly ofT scale.
In letrahedral complexes, there is no center of symmelry and thus orbitals have
no g or 11 desianation. However. the atomic orbitals from which the e and 12 orbitals
are derived do have parity properties that have a bearing on the molecular orbitals.
The nonbonding" orbitals are purely metal d atomic orbitals
11.21) and hence
retain 'their K character even in the complex. The molecular orbitals. on the other
hand. are formed from atomic d 11/trade) und p (wngerud(') orbitals. ThrouBh this
d-p mixing. which imparts some 11 character tO the t. level in the complex , the Laporte selection rule is
As a result , eMinction coefficients for tetrahedral comarc about 10! Bremer than those for
ranging from
to
IOl L mol- 1 em - .
A second selection rule states that <lny trOtLfitimfar ll'ltic'h
1> 0 is forbidden;
i.e .. in order to be allowed. a lransition must involve no change in spin state. Looking
al the correlation diagram for a
configuration in on ocwhcdratlield (Fia. 11 .35), we
note that the around state has a multiplicity of J (S .. I) and that there are three
excited slates with this same multiplicity: 1 T2z.
and lT111 (from the 1 P). Thus we
can envision three transitions that are spin allowed:
as
Jr,, 3
Tt 11
lT1"
40
--+
A2z
T 111(P)
"Aitaniomlsaruqual. but som< an:

Br:M:e. and Worlcl: New YCIC't, I946.
tMIIOChon." Orwd, Ci. Alt/mDI Furm; Harcowt.
Electi'Oflic Spectra af Camplexes
439
Transitions from 3T1,. to any of the singlet excited states are spin forbidden. A d 2
octahedral complex should, therefore, give rise to an dectronic spectrum con.sisting of
three absorptions. This will be true whether the field is weak or strong. However, it
shoulcl be observed that as the liefd strength increases , the separation between the
triplet ground and excited states becomes larger. Thus with increasing field strength.
transition energies become higher and spectral bands are shified toward the UV
region. For blue [V(H20)J3+. two of the three expected absorptions are observed in
the visible region (Fig. ll.38a): The transition to the 3 T:!II state occurs at 17,200 em-
and the transition to the
state is found at 25.700 em - . The transition to 3
is
calculated to be at 36,000 em - , but because it is of low intensity and is in the high
energy portion of the spectrum where it is masked by many totally allowed transitions.
it is not observed. In the solid state (V3 +/AI 20 3), this transition is seen at 38,000 em - .
The d' correlation diagram (Fig. 11.37d) is particularly interesting. The ground
state (11A 1.,) is the only state on the diagram with a multiplicity of 6. This means that for
a d' octahedral complex. ull transitions are not only Laporte forbidden but also spin
forbidden. Absorptions associated with doubly forbidden transitions are extremely
weak, with extinction coefficients several hundred times smaller than those for singly
forbidden transitions. I! is understandable. then, that dilute solutions of .Mn(ll) a re
COlorless and only with a substantial increase in ooncentration is the characteristic
faint pink color of [Mn(H10)J2 + observable (Fig. 11.38b).
The spin selection rule breaks down somewhat in complexes that exhibit spinorbit coupling. This behavior is particularly common for complexes of the heavier
transition elements with the result that bands associated with formally spin forbidden
transitions (generally limited tollS
l) gain enough intensity to be observed. Table
11.16 summarizes band intensities for various types of electronic transitions, including
fully allowed charge transfer absorptions, which will be discussed latet in the chapter.
If one's goal is merely to predict the number of spin-allowed tri.nsitions expected
for a complex, a complete correlation diagram is not needed. It is only necessary to
know the number of excited states having the same multiplicity as the ground state.
= ::
(nl
Mn2rd.s)
t0.36M MncCI04 11 1
(b)
0.05
an-
Fig. 11.38 Electronic absorption spcCif"d for (D) [VCHzOI,f+ and (bl [Mn(H 10),i. )From
Fiais. B. N . lntrodu<tion to Ugand H d ds; John Wiley: New York, t966; pP 221 and 224.
Used with petmission.l
440
11 Coordination O.emislry: Bonding, Spectra, and Magnetism
Table 11.16
Molar abso.,.tivities (*) lor
wcwious typ.. of eledranic
tnmsitions obserwed in
complexes
Type of
transition
Typical
c:omple..s
Spin forbidden
LapOrte forbidden
Mnny octahedral COfTlplexes

of d' ions, e.a .
[Mn(H 20).f+
Many octahedral complexes,
e.a.. (Ni(H 20)J+
Some square planar
complexes, e.a . (PdO..fSix-coordinnte complexes of
low symmetry;
square
planar complexes,
panicularly with oraanic
liaands
Some metal-to-lipnd charge
transfer bands in molecules
with U11$8lurated Jipnds
Acenbic complexes with
liaands IUCh as acac or
those hawill8 P, As, etc. as
donor a10ms
Many
transfer bands;
lranSitlona in orpnic
species
Spin allowed
Laporte forbidden
1- 10
Spin alowed
Laporte alowed
IOZ- tot
l..e,..,., A. B. P. lno'71ank EJrdrottk Sprclroscopy, 1nd ed.; Elsevier: New

. Yorlt. 15186; Olapter 4.
Table 11 . 17 summarizes this information for weak field octahedral and tetrahedral
complexes. Octahedral complexes hnvina d 1 d4 ,
and d'i configurations and weak
field ligands should each give one absorption correspond ins to!:.,. Configurations d 2 ,
d 3 , d 7 , and d' in weak octahedral fields each have three spin allowed transitions. (In
each case t:., is the energy difference between adjacent Al.<' and T,_.terms.) As we have
already seen, there are no spin allowed transitions ford' octahedral complexes having
weak field lisands. We shall see later that other factors, such as spin:-ocbit coupling
and Jahn-Teller distortions. often lead to more complex spectra than predicted with
the spin selection rule.
Another popular way of representing ground and excited siDles of the same
multiplicity for a particular configuration is with Orrtl d;agroms. Like correlation
diagrams. they portray the energies of stales as a function of field strength; however,
Orgel d iagrams are much simpler because excited states of multiplicities different from
that of the ground state are omiued and 011fy wtok field cases are included. An Ofl!el
diagram for Co2 (d7) in tetrahedral and octahedral ligand fields is shown in Fig. 11 .39.
Once again, we see the inverse relationship between the two symmetries, which arises
because a tetrahedral field is. in effect. a negative octahedral field . The diagr.lm also
iUustrates the effects of mixing of terms. As a aeneral rule, terms havina indentical
symmetry Will mix, with the extent of mixing being inversely proportional to lbe
enefiY difference between them. For Col+ the terms involved are the two r1
(tetr.lhedral) and 4 T1Jt (octahedral) levds. Mixina of terms exncuy parallels the mixing
of molecular orbit.als we encountered earlier (Chapter S) and it leads to an idemtical
tr.
Electranie Spectra of Camplex..
441
Tal.le 11.17
Ground ancl emtecl t.,s
ha-.ing the same spin
muhiplicities for weolc field
octaheclral [oct) ""d
tetrahedral (tel) c-plexes
bcitecl twith the -ltiplicify 01 the
Canfigurotion
opin
term
1:..,,
d 1 oct, tfi tet

dz oct, d 8 tet
d 1 oct. d 7 tet
d" oct , t? tet
d 5 oct, d 5 tel
oct. d 4 tet
d 1 oct. d 3 tel
oct, dz tet
d' oct, d 1 tet
JTliRI' l Az(NJ JTI(NI(P)
r ll r,(/t,(F). r,wCPl
'rl(,,
None
.r
'Ez.,,
,r
1 Tl!RI 3T w(F), JT u 1Pl

1
1 1
TM A2 1.to
ZT:t(RI
The g Slbsaipu are llllll'Opriate only for octahedralllereocllemisuy.

The (Fl and (P) nolBiions dtsipalt: the free ion torrn from which the
listed rmn
result: The upper level is raised in ene11y wflile the lower level faUs. This is repre4
sented in the Co2 + dillgram as divergina lines fo r the pairs of 4 T1, and T1 levels; the
condition of no mixing is shown as dashed lines. Note that for the tetrahedral case in
the absence of mixing, the two 4 T1 terms gradually approach each other in e nergy as
the field stren&th increases while just the opposite is true for octahcdrnJ complexes. As
a result. the extent of mixing is greater for tetrahedral complexes.
Orgel diagrams provide a convenient means of predicting the number of spin
allowed absorption bands to expect in a UV/visible spectrum for a complex. From
Frg. 11.39, it is clear that a
of Co2+ (or any other d 1 ionl should produce a
spectrum with three absorptions. A more general Orgd diagram pertainins to high spin
octahedral or tetrahedral complexes of metals with two to ei&ht d electrons is shown in
Fig. 11.40.
Up to this point we have considered two central issues Involved in interpreting
elect ronic spectra of transition metal complexes- the number and intensities of spectral lines. There is a third important spectral feature. t he widths of obser ved bands.
which we have not yet discussed. Consider again the visible spect rum for
rog. 11.39
for lhc
10.000
Orgel lliagt:lm
eo> ion in
tetrahedral llefll and

octahedral lrishtl fields.
The dashed lines represerll
the 4 T1 terms before
mixing. [From Orgel . L. E.
J. Cfl,m. Plry<. 19SS. 1J.
c- ;- __ _
7
1004-1014. Reprolluccd
with penniSliion.l
-1.000
-)00
Oq(om- 1)
)00
t.OOO
2.ooo
442
11 Coordination Chemistry: Bonding, Spectra, and Magnetism
r4
o.
dl
d)
1-----
0q - - - o--- Dq
Fig. 11.40 Orgel diagram ford'. J', J 1 und

(From Lever, A. B. P. lnOI'gonic
1986: p 8S. Used with permission.)
tf ions in octalledrol und tetrdhedrnllields.

Znd ed.; Elsevier: New Vorl<.
[Ti(H 2 0)JJ+ (Fig. 11.8). The single absorptlon band is quite broad, extending over
several thousand wave numbers. The breadth of the absorption can be altributed
mainly to the fact that the complex is not a rigid, slntic structure. Rather, the
metal-ligand bonds are constantly vibmting, with the result that an absorption peak is
with slightly different molecular structures
integrated over a collection of
and a.. values. Such ligand motions will be exaggerated through molecular collisions in
solution. In the solid state, however, it is sometimes passible to resolve spectral bands
into their vibrational components.
Sharp peaks also occur in solution spectra when the transitions involve around
and excited states that are either insensitive to changes in a.. or are affected identically
by the changes. These terms will appear on energy level diagrams as pamllel lines.
which will be horizontal in the event that energies are independent of 11.,. This is the
rationale offered. for example. for the relatively sharp peaks (a few hundrw em - in
width) observed in the spectra of Mrr complexe.s {Fig. 11.41).
Two additional factors that can contribute to line breadth and shape are spin-orbit
coupling, which is particularly prevalent in complexes of the heavier transition metals.
and departures from cubic symmetry, such as through the Jahn- Teller effecl. This
Iauer effect, which will be discussed later in this chapter. is believed to be responsi
ble for the low-frequency shoulder observed on the absorption line for [Ti(H!O!J2+
(F'tg. 11.8).
Tanabe-Sugono
Diagrams
In order to treat fully the problem of interpretation of spectra, it is common to use

dinarnms provided by Tanabe and Sugano. which provide on alternative means of
depicting the variation of term energies with field strength. Tanabe-Sugnno diagrams
Tanabe. Y .; Supno, S. J . Phys. Soc. Jpn. 1954. 9, 1SJ-166. 166-119.
Spectro of Complexes
443
O.lS
l.
0.10
o.os
fig. 11.41 Absorption spectrum for
Mnf't. Note the IUitT'OW lines. !From Lever.

A. B. P.
Elt!crrortlc Sprctroscnpy; 2nd ed.: Elsevier. New York. 1986;
Used
with permission.)
include both weak and stron& fields and hence are more comprehensive than Orgel
diagrams. They are similar to correlation diacram s but are more useful fur extracting
quantitative information.
A simplified version of the Tanabe-Sugano diagrum for rf' octahedral complexes
is shown in Fis. 11 .42. H The groun\1 Slllte is aiWllyS taken as the abscissa in these
diagmms with the energies of the other states beins plotted relative to it. Interelectronic repulsion is expressed in terms of t he Racah parameters 8 and C. which are
linear combinations of certain coulomb and exchanae lntecrals pertaining to the
uncomplexed ion.l Accurate evaluation of these integrals is in general not feasible
and so these factors are instead treated as empirical parameters and are obtained from
the spectra of free ions . The parameter 8 is usually sufficient to evaluate the difference
in energy between states of the same spin multiplicity; however, both parameters are
necessa.ry for terms of dilferent multiplicity. A relationship that will prove to be quite
useful in analyzins spectra is that the dilference in energy between a free ion ground
state F term and an excited P term or the same spin multiplicity (as found for d 2 , dl,
d 1 , and d 8 configurations) is ISB. Energy () and field strength are expressed on a
Tanabe-Sugano diagrnm in terms of the parameter 8 as EJB and I:JB, respec.tively. In
order to repre>;ent the energy levels with any accuracy, it is neces.sary to malte some
assumptions about the relative values of C and B. The ratio C/8 for the diagram in
Fis. 11.42 is 4 .8 . For most transition metal ions 8 can be estimated as approximately
1000 em- and C
-48. More precise values are aiven in Table 11.18.
At weak octahedral fields, the
state for a tJ6 complex is ' Tz. which
oriGinates from the free ion 'D term (Fig. 11.42). Amonathe excited terms at the weak
1
1
field limit is a A 1., (from the free ion /), which falls precipitously in energy with
increasing 6, eventually displacinG 'Tb as the around term at i:JB
20. At this point
spin pnirins takes place, resulting in a discontinuity in the dinaram, marked by the
vertical line. From this boundary on. the low spin 1A t.t term remains the ground state.
"'A cocnpletc set orTanube-Sua>nO diollfVM is liven in Appendix G.

<> Occasionally 1he Slaler-Condon-Shonley poramettrs F2 and F4 are used imlead. 1bcir rdatloo to
the Racah
is B F2 - SF and C lSF
444
11 Cocwdinarion Chemistry: Bonding, Spectra, and Magnetism
Fig. 11.42 Moclilicd J" Tannbe-Supno diagram showi111 only the 'D. 'H. 'F. and 1/lenns.
Arrows represent spin uUowed transitions fOC" hish and low spin complexes.
The spectrum of any octahedral d 6 complex can be assigned with the help of
Fig. 11.42. For high spin species such as [CoFt.f-. the only spin allowed transition is
sT!I<.-. 5EN and only one absorption should be observed. Indeed the blue color of this
complex results from an absorption centered at 13,100 em- ..- For low spin Col+
complexes there are two spin allowed transitions at relatively low energies: 1A 1.w1
T111 and 1A 111 - 1T!,., There are additional spin allowed transitions at higher energies,
44
Actually
state is
by a Jahn-Teller elfect (page 4Sll resukintl in two peaks.
Electronic Spectra af Co...ple..a
Table 11.11
Fr.. ian ........s af
par-ers and C
1or gaseavs
tramifion metal iofta
r.. --'>
Canfigurat;an
lan
Jdl
nz
Jd)
yJ
Cr..
Sc+
y z+
cr
Mn..
Jtr
Jd'
3tf'
3d7
Jds
4d'
...r
4d'
4ds
.5d2
1
5d
5d.
5d.
cr
Mn1
Mnl+
Fe2
eo,
Co2
Nil+
Mo1
Rhl+
Rh1+
Pd1 +
Os,.
Re4
Ire+
Os'+
lr'
Pt..
Pt2+
718
861
1039
480
766
918
1064
830
1140
960
lOSS
445
c
2629
416.5
4238
28.SS
38.50
3430
367.5
3325
3901
1100
971
1041
4366
4831
610
i20
620
683
780
4002
2620
650
810
'/00
660
no
600
uver, A. B. P. /"ttlftk Ellrollic

Elsevier. New Yorl<.
1986; p liS.
bul lhey senerally are masked by totally allowed transitions and hence are not
observed. Because the slope of 1T2Jt chanses more rapidly than that of 1T111,the two observed peaks will be further apart in ene.rgy at larger values of 6 . The spectra of yellow
[Co( en),),. and green [Co<ox)1) 1 - IFill. 11.43) confirm these expectations .
Fiuing an observed spectrum to its corresponding Tannbe-Suaano diagram enables one to obtain the value of l!. for a complex. In addition, it is possible to evaluate
Rg. 11.43 Spectra or
(Colen),)1 1-l and
1-J. [From
Mead, A.
Forllflay
Soc. 1934, JO, 1052-1058.
Reproduced wirh
permisaion. J
446
11 Coordination Chemistry: a.,..ding, Spectro, and Magnetism
the electronic repulsion pammeter B. The apparent value of Bin complexes (referred
to liS B'} is always smaller than that of the free ion. This results from a phenomenon
known as the nephelauxetic effect and is auributed to delocalization of the metal
electrons over molecular orbitals that encompass both the metal and the ligands. As a
consequence of this delocalization or "cloud expanding, the average interelectronic
repulsion is reduced, making B' smaller than B. The nephelauxetic ratio, {3, is given
by:
(11.17)
{3 = B'/B
The value of {3 is always less than one and it decreases with increasing delocalization.
There are several approaches 10 extracting information from a Tanabe...Sugano
diagram . One is to fit observed transition energy ratios to the diagram and thereby
obtain a value for 6./B. The accuracy with which this can be done by hand depends to
some extent on the precision of the Tanabe-Sugano diagrams that are used . With
small versions such as those presented in Fig. 11.42 and Appendix G. accuracy is
limited. but nevertheless they can be used to illustrate the principles of fitting. The low
spin complex [CO(en)1f ' will serve as an example. Its spectrum (Fig. 11.43) shows
two bands. at 21.550 em- and 29.600 em-. which are assigned as follows:
21.550 em-
1
A, 11
29.600 em-
T2JI
The ratio of these two energies, given by

1A , - 1T2JI
1
A , , . - T111
_ 29,600 em- _
I - I.37
21.SSO em
(11.18)
can be fitted to the diagram (Fig. 11.421 by sliding a ruler along the abscissa until a
point is found at which the measured energy level separations have this same ratio.
This is achieved at 6./B
40. At this point. the value of EIB (actually EIB') for the
lowest energy transition can be read from the diagram as 38. or:
A 1, - 'Ttf
B'
21.5.50 em- ;.,

38
B'
(11.19)
Solving for B' yields 570 em -. which is much smaller than B for the free CoH ion
(1100 cm- 1) given in Table 11.18. Finally. ll can be calculated from 6./B' (40) and
B' (S70 cm- 1) . The result. 23.000 em-, is in very good agreement with the more
precise value (23,160 cm- 1) found in Table 11.6.
The spectra of the three c,.J+ complexes shown in Fig. t 1.13 may be analyzed
similarly. The splitring of F and 4 P terms. including mixing of the two states, is shown
in Fig. 11 .44. The value of 11 is obtained directly from the spectrum as the energy of
the lowest energy transition (v 1}. When all three transitions are observed. it is a simple
mauer to assign a value forB' since the following equation must hold:
(ll.lO)
where the absorption frequencies increase in the order v 1 < v2 < "3 For example, the
value of B' for the lluoro complex is:
B'
n(34,400 + 22,700 - 3{14,900)] = 827 em -t
(11.21)
If only two transitions are observed (as. for example, in Fig. 11 . 13b where v3 is
obscured by a charge transfer band). it is stiU possible to evaluate B' by other
447
Eledronic Spedra of C0101plex
.,T_____,.,.
Fig. 11.44 Splittir& oi'F
Mt.lnc
Md p rums in
L----'T,, CP)
mixins ur
r,. rerms.
_L , t--- J,-----\
----r,.
ISB
- - -' T,.CFl
'F
11n
ocrohedrol field. Note
0.6t._
(-----
I.U.,
O.U.
\ I
-----'A,.
melhods ..., Once values ror 6 and 8' have been determined. it is possible to estimate
all the transition rrequencies ror a com plex. The appropriate relationships ror high
spin oclnhedral d 3 and d 1 and tetrahedral d 1 and d 1 species are:
or
(11.22)
v1
Vz
At. -
T ,M(F) -
(6)! - 18.08' 6 )1
( 11..23)
+ l[22S8 '1
+ (6)! - 18.08' 6)1
(11.24)
1.58' + 1.56 - lllli8' +
T 1,(Pl = 7.58'
"l
+ 1.56
These equations. which c:1n be solved by iterative proce.s ses .u. lead to accurate
estimateli or transition rrequencies (Table 11 . 19) and quite satisfactory fitting
spectra. Parallel equations ror octahedral tf' complexes
or
.., = 6
v2
Table 11.19
Calculated end
P.....,.al
lransilians
chr"""u....lll) c - p l -
- 48'
868'2 /!i.
(11.25)
+ 12B' + 28' /6
(Crf.Jt-
Energy ......
dingrom
r,;FJ
( 11.26)
(Cr(ox),),_
(C.{en)a),.
up.
Cole.
&p.
Calc.
34,800
34.400
311. 100
22,400
22.700
24.000
23,900
28.700
28.SOO
14,900
14.900
17.SOO
17,SOO
21 .850
21,800
..
Calc.
Exp.
46.SOO
Tllis tramition is not upc:rimcnlaly obsetYcd becuusc il is maslced by the chlqe transfer
apectrum.
4J Le..,., A. B. P. 1 . Chm. EJ11c. 1961. 45. 711-712.

.. Brown. D. R.; Pavlis. R. R. J. Chtm. U/tlc. 1915, 62, 1107-1108.
..
448
11 Coordination Chenoistry: Bonding, Spectra, and MagMiis111
Tetragonal
Distortions from
Octahedral
Symmetry
We have seen that the electronic spectra of octahedral

and tetrahedral ML.
complexes may be analyz.ed with the aid of appropriate correlation. Orgel. or TanabeSugano diagrams . When we move away from these hiahly ordered cubic .structures to
complexes having lower symmetries, spectra generally become more complex. A
general consequence of reducing the symmetry is that energy levels that were degenerate in the more symmetric geometry are split . With more energy levels, the number
of possible transitio ns increases und so does the number of spectral bands. In this
section we will examine departures from octahedral symmetry in six-coordinate
complexes.
There are a number of circumstances that can lead to a symmetry that is less than
octahedral in a six-coordinate complex. One is simple replacement of some of the
liaands of an ML6 molecule or ion with liaands of another type. For example, if we
replace two L groups to give either cis- or tran.s-MX2L 4 , the symmetry becomes C2 or
D41t respective.ly. More subtle alterations in symmetry frequently occur in complexes
having bidentate or chelating ligands. For instance, the chelated complexes.
[Cr(en)J.i 3 and [Cr(ox)3)3 - are not pe.rfectly octahedral. Because of the rings associated with the bidentate ligands, these complexes belong to the lower symmetry point
aroup D3 Neverthdess, the perturbation is slight enou&h that we were able to
successfully analyz.e the spectra of these complexes (Fig. 11 . 13) as though they were
purely octahedral. and the expected absorptions for a symmetrical [Cri..J 3+ species
were observed. However, if one of the ethylenediamine ligands of [Cr(en)3)l+ is
replaced with two r ligands to Jive tran.r-(Cr(en)1 F 2)+, t.h e change in symmetry is
drastic enough that to treat the new complex as pseudooctahedral is no longer valid;
rather, it must be analyz.ed as a tetragonal (D4,.) species. The alteration in energy
levels that accompanies this prosression from octahedral to tetragonal symmetry is
shown in F"rg. 11 .45. Each of the triply degenerate T terms is split into two new terms
(an E and an A or 8), with the result that six transitions are now expected instead of
three. The four lowest energy absorptions for trans-(Cr(en),F2)+ are shown in Fig.
------,.-',
Rg. 11.45 Alteration or

tnttBY levels for :l d' ion liS
the symmetry of its
environment changes from
OCiahcdral (0) to
telr3Jonal (D41,).
--,r+-1- 'A,.
"T,, - - - --< :: =
--
--
- --..+1+ ",
.---...-144-11- 8)1
Electro..ic Spectra of Complexes
449
1.0 1-
....
..,
.. , .
'
'il
,,'
.......
.!I
//
----....... . ...
I
----i
.......
......... /'
I
'
...,
,l '.
\\
\.,:
_./
JO
..
..
\ ...
\ :,
20
fnq\omcy (cm' 1 x tO" J)
Fig. 11.46 EJecuonic Sf)CWUm of traiiSo{()(en),F:}"; transition frequencies arc pw:n in

Table 11.29. (Modified from Dubicki, L.; HitChman. M. A.; Day, P. lllarf.
1,0, 9,
IIIS-290. Used witb permission.)
11.46. A firth band appears as a shoulder in lhe charge transfer resion and lhe sixth has
been calculated (Table 11.20).
Tetragonal distortion from octahedral symmetry often occurs even when all six
ligands of a complex are the same; Two l &roups that are trans to eac h other are found
to be either closer to or farther from the metal ion than are the other fo ur ligands. A
distortion of lhis type actually is favored by certain conditions described by the
Jahn-Tel/er
The theorem states that for a nonlinear molecule in an electronically degenerate state, distortion must occur to lower the symmetry . remove the
degeneracy, and lower the energy,., We can determine which octahedral complexes
Tolole11 .20
Sp.ctral clala for tron
(Cr(en) 2F:z]CIO. at 4 K
18,SOO
21,700
25,300
29,300
4 1,000 (shoulder)
43,6SS (calculated)
n Jabn, H. A.; Tdler.
E. Proc. R. Sue. Lottd. IJJ7,A/6/, 220-22S.
1931, A/64, 117-l)t.
H. A.. Proc. R. Soc. lAM.
450
11 CaordinotiDft Chemistry: Bonding, Sp<octra, and Magnetism
Table 11.21
Canfigurolians for ""'idt
Jahn-Teller cliolortions are
.-pected in ML. complens
C....figurvlion
Grouncl-ttate t"""
2T.
d'
d2
d'
d.
T,,.
' EN (high spin)

3
T1,. (low spin)
6
A'" (high spin)
(low spin)
(high spin)
1
A 1N (low spin)
(high spin)
2EN11(low spin)
d'
'T
d7
T,
d8
'A
2
tfi
E,
Jafu>-Telw c5slartian?
Yes
Yes
No
Yes
Yes
No
Yes
Yes
No
Yes
Yes
No
Yes
will be subject to Jahn- Teller distortions by considering gTOUnd state degeneracies.

The Tanabe-Sugano diagrams in Appendix G reveal that the only configurations
6
having nondegenerate ground states are d 3 ( 4 A 211) , high spin d'
1) . low spin d
8
1
{ A 1) , and d (1A2 N) . Thus spontaneous Jahn- Teller distortions are expected for all
other configurations: d 1, d 2 , d 4 ,1ow spin d'. high spin dt.. d7 and d 9 (Table 11.21).
Basic insight into the nature of the Jahn-Teller effect can be obtained by returning
to an orbital picture. Consider Fig. ll.47a in which the two ligands on the z axis of an
Fig. 11.47 Alter&ion of

octahcdrul orbital energies
I
I
(center) under tetrogonal
distor1ion: (a) l ligands

out; (b) lligands in.
-x
Drawing is not to scale;
.'
ll..>> 8, >
xy
a,{ -'I,a,
x:.y:
x:. y:
xy
(a)
60
-+--'-z.__
0>)
IJ:.
Eleclroaie Spectra of Cnmplex..
451
MLh complex have moved llWlly fro m the centrul metal. In so doing, they have
reduced their interaction with the metol d orbitals th:!t have a t component, i.e., the
Because of the "center-ofgravity" rule:the orbitals without at component, the d,;_ : and
will be ruised a
corresponding amount. It is not possible, a priori, to predfct the magnitude of these
splillings because the extent of distortion cannot be predicted. However, we can say
that the spliuing of the strongly antibonding
orbitals (S 1) will be significantly
larger than that of the 'lll orbitals (c52) because the Iauer are either nonbonding or are
involved in weaker 'TT interactions with the ligands. Also, both S 1 and
will be
relatively small with respect to A,., so we are justified in regarding the distortion as a
perturbation of an octahedral geometry.
The Jahn-Teller theorem per se does not predict which type of distortion will take
place other than that the center of symmetry will remain. The t ligands can move out
as in the example discussed above or they can move in. For a "t-in" distortion, the
splitting pattern is similar to that observed for a "t-out." but the energy ordering
within the tt11 and
levels is inverted (see Fie. 11.47b).
Consider a complex that is subject to Jahn-Teller di.s torlion, (T.Cttf-. The Tr
ion is a d 1 species and the 10 around term which arises from it in an octahedral field is
split into 1 T21< and 1 11 terms . The 1T21< term is the ground state and, because it is triply
degenerate, the Jahn-Teller theorem would predict a distortion .a The Structure or
(TiOJ1 - does show a slight compression or the axial ligands at low temperature. but
this is thought to be due to packinc forces ruther than the J ahn- Teller effect. Evidence
for a Jahn- Teller distortion is seen, however , in the electronic spectrum of the
complex. There are two absorption peaks separ.ucd by approximately 1400cm-, one
resulting from excitation or an electron from the around Stole eslll) to the excited 28 111
state and the other to the excited 1A 111 state (Fig. 11.48),4Y This
is supported by EPR results. which are consistent with a tetragonal compression. For some
d 1 complexes. the Jahn-Teller splilling is not of sufficient magnitude to produce well-
d:>, d,.,.. and d..,. As a result, these orbitols are
'
e;
Fig. 11.48 Electronic

sc>eetro of
til.
Cs:KlTiO..I 1111. and
Rb,(TiCI..I tllll. [From
Ameis. R.; Kremer. S.;
Reinen. 0 . '""'II Clrrm.
1!1115. 24.
Used
with permission.!
.. In thinking llboul dqcnct11C)'. It is

10
between terms and ortitals. Fer
example. ad' tonliplraliof1 ter'l lives rise to three ettrons occupying the J"'' J.,, and J,
in an octolledtal complc>. AllhouJh the lhrtc ortitals arc <!ev<:ncratc, the 10<MC) SJale term
for lflis
is 4 Al.t which is nondqcnernte. Thus, lle5pilc I he <kactw!r:IC)' d the atii;)Js,
no Jahn-Tdcr distortion would be prc:dictocl for thill
"'Amris, R.; Kremer, S.; Rcincn, 0 . lno<f.
19$5, 24, 27St-27S4.
452
11 CGardinatlon Chemistry: Bonding, Spectro, and Magnetism
separated bands in the electronic spectra. A case in point is

for which
the two absorptions appear as one broad peak with a low-energy shoulder (Fig. 11.8).
As we have seen (Table 11.21), all of the ML6 complexes that are susceptible to
Jahn-Teller distortion have octahedral configurations that involve asymmetric electron occupation of either the or
orbitals. Generally speaking, the former leads to
considerably more pronounced distortions than does the latter. This occurs because
the level is much more involved in the bonding than is the t2R . Hence complexes
with 1 or 1 configurations (from high
and tf>, low spin d 7, or d") often
exhibit substantial distortions . It is not uncommon for these complexes to have bond
le.ngth differences (two longer and four shorter or vice versa) that can be detected
crystallographicaQy at mom temperature. In fact, some of the strongest evidence for
Jahn-Teller effects in transition metal compounds comes from structural studies of
solids containing the tP Cu2 + ion. DistOrtion by either elongation or compression will
lead to stabilization of a copper( II) complex. However. experimental measurements
show that the distortion is generally elongation along the l axis (Fig. 11 .49). Table
11.22 lists some bond distances found in crystals containing hexacoordinate Cu(ll)
ions. Each compound has both shorter and longer bonds. It is of interest that the
"shOrt" bonds represent a nearly constant radius for the Cul+ ion, whereas the
"long" bonds show no such constancy. This sugge.s ts that the short bonds represent a
lower limit or starting point from which various degrees of distortion in the fonn of
bond lengthening can occur.
We have fewer data to support Jahn-Teller distortion in high spin d 4 or low spin
d 7 complexes. Chromium(ll) and manganese(IJI) are d 4 ions, and both have been
found to be distorted in some compounds (see Table 11.22). Furthermore, extensive
studies of six-coordinate manganese(lll) compounds have shown that their spectra
can be readily interpreted in terms of elongation along the l axis . The d 7 configuration
of low spin Co2 + is less straightforward. With ligands that are sufficiently strong field
to induce pairing, the ion tends to form five- or four- rather than six-coordinate complexe.s. For example, the expected hexacyanocomplex, [Co(CN)J"-, is not found. but
instead the principal species in solution has five cyano groups per cobalt and is probably
1Co(CN),H20)3 -. This might be viewed as an extreme form of Jahn-Teller distortion,
namely complete dissociation of one cyanide from the hypothetical [Co(CN)J'- ion.
Six-coordinate Co2 + complexes are observed for the ligands bis(salicylidene)ethyJ..
enediamine (H2salen) and nitrite. The spectra for these species are quite complicated.
but they are consistent with axially elongated structures.
e;
e;
e; e;
Fig. 11.49 Orbital energy

lc:vd diagrams for d 9
conlisuration in octahedral
(0.) and
tetrasonal
(D..) fields.
Electronic Speclro of Complex.
453
Table 11.22
Some typical -'<d-ligond
diotan- in
Cr(ll).
eurm.
o,d Mn(lll) campounda
Compcuncl
Shoo1 clistanc..
rM
Longct-.a
rM
CuF2
CuF2 2H 20
4F at 193
2F a1 190
20 al 194
4Fat 191
4Fat 192
2F al 188
2Fal 197
2Fat 189
2Fat 196
40 at 230
2CI at229
20at 196
2N at 202
2a at 228
4N at 1JJ7r
4F at 200
2F at 200
2F at 179
2F at 191
4Fal 183
122
119
121
2F at 227
2F at 247
156
176
2F at 237
2F at222
2F at 226
166
lSI
2F at 225
154
20 at29S
196
19S
KzeuF.
NaCuFJ
KCuFJ
CuC!z
CuClz2H1 0
CuClz2C,H,N
Cu!NH,):
CrF2
KCrF1
MnF3
K2MnF,H20
121
117
126
118
125
131
130
123
127
129
132
119
119
108
120
112
ISS
20 al294
2a at 30s
2N at 262
2F at 243
4F at 214
2F at 209
2F at 2ff1
206
187
172
143
138
136
Data, lll1less olherwisc nolcd, &om Wdls, A . F. Struclwo/lfiOI'IOnk

CMmisrry, Sth cd. ; Oxford Uni..r:rsity Prtss: London, t986. Wells lilts ""'"Y
addilianal clala.
6 AD distances are
aublracting the covalerlt radius
M- X dislanc:e.
The ndWs of the metal wu oblalncd by

or the liptinJ atom (Table 8.1) from the
Tlllla'. T.; VaaJ)>ao, P. A. / norf. Ch-. 1967,6, t26.
Complexes having measurable bond-length differences, such as those reported in

Table 11.22. are examples of staric Jahn-Teller behavior. In some other complexes,
no distortion can be detected in the room tempernture crystal struct ure. but additional
evidence shows that the Jahn- Teller effect is nonetheless operative. The supplemen
tary evidence may consist of a low-temperature crystal structure showing distortion or
spectroscopic data consistent with tetragonal aeomctry. These complexes are display
ing dynamic Jahn-Teller behavior. In its simplest form. this can be thought of as a
process in which a complex oscillates among three equivalent tetragonal structures. At
any instant, the complex is distorted, but if the oscillation between forms is rapid
enough. the strucrure observed by a particular physical method may be time-averaged
and therefore appear undistorted. Sometimes cooling a sample will slow the oscillations enough that a single distorted structure is "frozen out." In some instances.
however, a distoned structure produced upon cooling does not represent a true sralic
condition but rather a different form of dynamic beh:lvior.
There is an interestina series of compounds, all or them containifll the hexanitrocuprate(ll) ion ({Cu(N02>t/-), which exhibit lhe full range of static and dynamic Jahn-Teller effects described above.j() In some members of the series, such as
,. Ha!h:lway B. J . Sfrlld. &ndillt (Bnl'ml 1984, S7, S4-tta.
454
11 Cootdinotion Chemistry: Bonding , Spectro, and Magnetism
and
Cu(IJ) anions are elongated at room temperature (298 K), while in o thers. such a.s K2 Pb[Cu(NO..JJ.they are
undistorted. In yet a third category are Cs2Ba[Cu(N02)J and
ror
which the room temperature structures appear to be axially compressed octahedra but
actually are the dynamic avernges of two tetragonally elongated structures. Upon
being cooled to 176 K.
also assumes this "pseudo compressed''
geometry. The subtle structural variations in these and other complexes exhibiting
similar behavior have been elucidated with a combination of physical methods, most
ofte.n crystallography in conjunction with EPR and electronic spectroscopies.''
No discussion of the Jahn-Teller effect in coordination compounds would be
complete without including the special features of chela ted compounds (see Chapter 12
for a more thoro ugh discussion of chelated complexes). The very nature of the
chelated ring tends to restrict the distortion of n complex from a perfect octahedron
because the ligand will have a preferred "bite" or distance between the coordinating
atoms :
An example of the conflict between stabilization from the Jahn-Teller effect and
c,helate ge.o metrical requirements is found in the ethylenediamine complues of Cu2 ...
Most divalent transition metal ions form complexes with ethylenediamine (enl by
stepwise replacement o r water:
(M(H 1 0 )6]H +en
[M(H 20)4 en]1+ + en
(M(H 1 0)4 enr
+ 2H 10
[M(H 2 0h(enh]l+ + 2H 2 0
[M(H 1 0h(enh]H + en __..... [M(en),]l+ + 2Hl0
(11.27)
(11.28)
(11.29)
Each step has associated with it an equilibrium or stability constant. K 1, K!. or K 1

which measures the tendency for formation of 11 mono. bis-. or tristcthylenediamine)
complex, re.s pectively. The values of these const ants fo r the ions Mn 2 to Zn! show
a rather uniform trend of gradually increasing stability from left to right across the
series (the Irving- Williams o rder) (Fig. 11..50). The Cu2 ion provides a striking
exception. ho wever. with the uis(et hylenediamine)copper111) complex. [Culen)1 J2+.
being remarkably unstable. In fact, at one time the very existence o r this species was
questioned. Although it was subsequently prepared.n the value of K 1 (a measure of
the tendency to add the third ethylenediamine ligand) is the lowest of the ions in the
series even though the K 1 and K 1 values are the highest . This lack of stability for the
tris complex can be traced directly to the tendency ror a six-coordinate dv ion to
undergo distortion. The bis(ethylenediamine) complex. [Cu(en)2 (H2 0)2 ) 2 +. can distort
readily by letting the two trans water molecules move out from the copper. lea vine the
J. H.: Blqj. H. B.: Camp. E. : Mcyer..s-lrin. V.: Jenscn. W. P. lnorx. Cbmt. t919. 18.
7)}-7.50.
Gonb>. C.: BinlwhiSiel. R. K. I . Am. Chtm. Soc. 1.959, 81. 3567-3S69.
Fig. 11.50 Stepwise

stability constants. K 0, K,.
and K3 , for ethylenediamine
complexes of several firstrow transition metals in
aqueous solution.
'<
<>.
I
Mn.,
Fe 1
tli''
two ethylenediamine rings relatively unchanged. In contrast, !he Iris(ethylenediamine)

complex cannot distOC't tetragonally without straining at least two of the chelate rings:
(11.30)
Alternatively, it is possible that the constraint of a chelate ring system can prevent
tetragonal distortion altogether, but the resulting perfectly octahedral complex will
lack the stabilization inherent in Jahn- Teller distortion . Despite the restraining inlluence of a biden tate ligand, a number of distOC'ted chelated structures are known . FOC'
example, [Cu(bpy)(hfahl is known to be tetragonatly distorted." Both bipyridine and
hexnlluOC"oacetylncetonate are chelating ligands that form bonds through nitrogen and
oxygen atoms. respectively. The structure of this molecule is shown in Fig. II .St. The
two nitrogen atoms of bipyridine bind to the copper at a distance of 200 pm. consistent
with the short bonds from other nitrogen ligands to copper(IJ) (Table 11.22).. One
oxygen from each hexnfluoroacetylacetonate ligand binds at a distance of 197 pm,
again consistent with short Cu-0 bonds. The two remaining oxygen atoms fOC"m
Cu-0 bonds which are some 33 pm longer. indicating severe Jahn-Teller distortion.
Charge Transfer
Spectra54
Although most of the visible spectra studied by inorganic chemists in evaluating

coordination compounds have been of the d-d (or ligand field) type, perhaps more
"bpy - 2.2'-bipyritlinc: -
00
hfa heJwJluoroacctylac.ctOPate, (CF,C(0)CHQO)CF31- ( I.I ,I..S.S.S.hcxnllll<lropcntane2.4-dlonotet.

,.. Lever, A. B. P. lnorRunk
Spectroscopy, 2nd .,d.; Elsevier. New Vorl<. 1986; ChapterS.
Lever. A. 8 . P. J . Chmr. Educ. 1914. j/, 6t2-6t6.
456
11 Coordination Chemistry: Bonding, Spect.o, nnd Mogneaism
Fig. 11.51 Slruclure of

(CII(bpy)(hfnl.:J showing
Cu-0 and Cu- N bond
lengchs (in picomelers).
(From Veidis, M. V.;
Schreiber. Cl . H.; Gough.
T. E.; Palenik. G. J . J . Am.
Chem. Soc. 1969. 91. 1859.
Reproduced wich
permission.I
important from an applied standpoint have been those involving charge transfer
transitions. As the term implies. these transicions involve electron transfer from one
part of a complex to another. More specifically. an electron moves from an orbital that
is mainly ligand in character to one that is mainly metal in character (ligand-to-metal
charge transfer, LMCT) or vice versa (metal-to-ligand charge transfer, MLCT). Unlike d-d transitions. those involving charge transfer are fully allowed and hence give
rise to much more intense absorptions (see Table 11. 16). When these absorptions fall
within the visible region, they oflen produce rich colors and therein lies the source of
practical interest in these types of transitions."
In a primitive sense, a charge transfer transition may be regarded as an internal
redox process. This makes it possible to use familiar ideas. such us ionization energies
and electron affinities, to predict the conditions that will favor such a transition.
Consider a crystal of sodium chloride. Imagine ionizing an electron from a chloride ion
(l:t.H = electron affinity) and transferring it to the sodium ion (l:t.H - negative of
ionization e.nergy). It could be imagined that the overall energy (including - U0 )
required to effect this process might be supplied by a photon. Indeed such photons
exist. but their energy is so high chat they belong to the ultraviolet portion of the
spectrum. Hence, sodium chloride does not absorb visible lighc: It is colorless.
Now consider how we might modify the metal-ligand coml:lination to make the
electron transfer from ligand to metal more favorable . We would want a metal with a
relatively high ionization energy so chat it would have empty orbitals at fairly low
energies. Good candidates would be transition or posttransition metals. especially in
higher oxidation states. An ideal ligand would be a nonmetal with a relatively low
dectron affinity. which would mean that it would have filled orbitals of fairly high
energy and would be readily oxidizable. Chalcogenides or heavier halides would be
examples of good choices. The nee result of such a metal-ligand combination would be
that the orbitals involved in an LMCT process would be close enough in energy that
the transition could be induced by a photon in the visible or near-ultraviolet region.
The permanganate ion. Mno;. meets the criteria set forth in the preceding
paragraph: Manganese is in a formal oxidation state of + 7 and combined with four
oxide ions. The molecular orbital diagram for tetrahedral complexes in Fig. 11 .52
allows us to identify possible LMCT transitions. In any tetrahedral complex, the four
" For a discu$.<ion oC color arising from charge lr.JnSrer cransilions. see Nussau, K. 1M Phy<ks and
of Color; John Wiley: New York. 19113; Chapler 7.
,,,
,"' r
,"
/
r.,
.,
__,,,
,,,,
Jl
ln+ U p - .
,.
.r--;
"''' oj \
I I
/.
,,
,,
"'/
''
,,
," ,'
/
\,' .,.i'
(n + l)1 _::l....j
\\
.,. .,.
''
'
II
\ ' \"l
I\
fj'
_...
II
'
1 1
' '
' \1'
\I
\\
r, '
'
''
\1
'
'
'\
11 12
",,
,,
.;
/
/,//
, ,"' /
1\-..2.-
,,
o,. 'z Col
Fig. 11.52 Molecular orbital diagram for U ICinlh.,drol Ml.... complcl'., showin& pOSsible
lipnd-lo-metul charge lransfu (LMCTllransilions.
lowest energy u-bonding orbitals will be filled and will be primarily ligand in character.
Next there are two sets or u-nonbonding MO's, one ligand-centered and one metulcentered. In permnngnnate, these orbitals would correspond to filled oxygen "P
orbitnls and empty manganese Jd orbitals, respectively. All of the higher energy
antibonding molecular orbitals would be unoccupied for a manganese(VII) complex.
HenCe there are four possible lil!llnd-to-metal transitions:
L(c,)L(c1) L ( c J - M(e)
L{r2 )
Mit;>
For Mn04 all four of these transitions have been observed: 17.700 em- (r 1 - e);
29,500 em- (1 1 - 4); 30,300 em- (t1 - e ); and 44,400 cm- 1 (r2 -+
Only the
absorption at 17,700 em- falls within the visible 111n&e ( 14,000-2B.OOO cm- 1), and it is
responsible for the familiar deep purple color of MnO;.
,. Lever, A. B. P.
SPtrote(lpy. 1nd ed.; Ellcvier. New Yon. 1986; p 324.
458
11 Coordination Chemistry: IGftding, Sped,.,, nnd Mag.,elis no
In a similar wny. the charge transfer spectrum uf oranae

ion can be
analyzed, the LMCT process being facilitaled by the hii h oxidation sllll.e of chro
mium(VI) . Many iodide salts also are colored because of charge transfer transitions or
this type . E)(llmples are Hgl 2 (re d), Bil1 (oronae-red), a nd Pbl2 (ye.Jiow). The metal
ions in these substances certainly are not outstandins oxidizing agents. but the
transitions occur because the iodide ion is easily oxidized.
If the energy difference between the lowest unoccupied molecular orbital
(LUMO) centered on the metal ion and the highest occupied molecular orbital
(HO MO) centered on the ligand is very small (less than 10.000 cm- 1) , to tal electron
transfer between the two may occur. This will be the case if the metal ion is a
sufficiently sood oxidizins aeenr and the lipnd a good enough reducing agent to cause
a s pontaneous redox process . The res ult is breakdown or the complex. Examples of
complexes in w hich this occurs are [Co(H1
and Fel l : Water is oxidized by Col
and the iodide ion is oxidized by FeJ . Despite the thermodynamic instability of these
complexes. howe ver, it has been possible to isolate both o f them by procedures that
take ad vantage of their kinetic ine rtness.n
Some e xamples of pigments that o we the nature and inlensity of their colors to
ligand-tCHnetal charge transfer transitions are listed in Thble 11 .2J . Some of these
have been long known and used by people in their efforts to beautify their immediate
environments. The use of ochres as pigments, dating from prehistoric times, foUowed
from their natural abundance [the reds and yellows of the deserts and some other soils
are caused by iron(lll) oxide). Pigments used in antiquity included orpimeot found in
Tutankhamen's tomb near 111tbes and lead antimonate (later dubbed "Naples
yellow"}, which was importa nt in Babylonian glazes." Later, vermillion became an
important pisment in the Venetian school of paintini. and chrome yellow continues to
be an important cclorina agent in several contexts because of its brightness.'9
0>J'
Table 11.23
Plgmem in w!Mch colar is
P"aduced by 5gandl.........,.
charge u-ler lr...,.;lions
.........
Cadmium yellow (CdS)
Vermilion (HgS)
Naples yellow (Pb3(Sb04 ) 1)
Massicot (PbO)
Chrome yellow (PbCrO,)
Red and yellow ochres (iron oxides)
Ligand 1r,.
Ligand 1r,.
Liaand
1r,. ---+
Upnd .,.,. ---+

Ugand .,.,. - +
Ueand 1r,. ---+
Brill. T . B. liJlltt. Ill lntn adion with Art und

Ycrt. 1980. U$Cd with permis1ion.
Simplifocd notation. Sec text lind
---+
---+
metal
metal
mellll
metal
metal
metal
Ss
6s
Ss or 5p
6s
3J
3d
Plenum: New
Fia. I Ul.
"The synthesO. of C.ICOIH:(li,JJSO.h 6H!O Ia reponed in Jollnson. 0 . A.;

A. G .
J . C1rrm. So..-. lA I. t %6. 7'JI!-801. ThcfW"cpor.llion ofFcl) bdcsa'bed in Yoon. K. 8 .; Koclli. J. K.
ltHXN. Chrm. 1990, .?9.1!69-874. This rcpon dispclcd a lonaklassumption thalllle compound
could not exist.
"' A Hislt>ry of
Vol. 1: From &tfy Tunrs to FnH of
Holmyard. E. J.; Hall. A. R . Eels.: Oxford: London. 19$4.
Empirts; Sint;cr. C. J.;
""For an inleresti"' discussion of iDOraanic piaments and tllac- relation to art, sec Brill. T . 8 . U/lht.
Its lntrra<'fiun -oith An unJ Antiq<itiu; Plcrun: New Yorit. 1!11!0.
Magnetic Properties of Ca"'pl_exes
459
6L
fig. 11.53 Simplified molec:ulat orbital diasnm ror an octahedral Ml.., complex showin11
possible melal-111-lipnd cllatJe transrer (MLCT) tnansitions wtlen both the lz. and ,; orbituls
are oecup;ed and the ligands have empty .. otbitols.
Charge transfer pmcesses in the opposite direction, from metal to ligand, are
favored in complexes that have occupied metaJ-c,entered orbitals and vacant low lying
ligand-centered orbitals. Prime examples are complexes in which the ligands have
empty w antibonding orbitals. Ugands falling into this category include carbon monoxide, pyridine, bipyridine,
and IJ phenanthroline. FiGure II .SJ shows possible MLCT transitions for an ocmhedrat complex in which both the t 2., and orbitals
are occupied.
e:
Magnetic
Properties
af
It should be quite clear from the foregoing discussion that electronic spectroscopy is a
powerful method for investigating transition me tal complexes. Additional and complementary information can be provided by magnetic measurements. Because complexes
generally have partially filled metnl d or f oroitals, a range of magnetic pr-openies can
be expected, depending on the oxidation s tate, electron configuration, and coordination n umber of the central metal.
60
f'tais. 8 . N. In COtriP'<Iwruh" CoorditroriOtO Ch,mistry; Wiltinson. Ci.; Gillard. R. 0.; Me

Oevaty. J. II., Ed$.; Perpmon: New Yooic, 1987: Vol I, OI;Jp(cr 6. Ciertodl. M. Mat:'f'lism attJ
Lif(UIIII-Firid Analysis; Ounbriclj;e University: New YO<lt. t91l. Cat1in. R. L MugMtoc:lwmisfry;
SpmacrVerla& New Yorlt. t986. O'CoMor, C. J. Prog. lnorg. Clwm. t 982, 19, 203-28).
460
11 Coonlination Chemistwy: Bonding, Speclro, a.,d Magnetiom
Substances were first classified as diamagnetic or paramaanetic by Michael Faraday in 1845, but it was not until many years later that these phenomena came lobe
understood in terms of electronic structure. When any substance is placed in an
external magnetic field, there is an induced circulation of electrons producing a net
magnetic moment aligned in opposition to the applied field. This is the diamagnetic
effect and it arises from paired electrons within a sample. Since all compounds contai"J
some paired electrons, dia111118netism is a universal property of matter. If a substance
has only paired electrons, this effect will dominate, the material will be classified as
diamagnetic, and it will be slighlly repelled by a magnetic field.
Paramagnetism is produced by unpaired electrons in a sample. The spins and
orbital motions of these electrons give rise t o permanent molecular magne tic moments
that tend to align themselves with an applied field . Because it is much larger than the
diamagnetic effect, the paramagnetic effect cancels any repulsions between an applied
field and paired electrons in a sample. Thus even substances having only one unpaired
electron per molecule will show a net attraction into a magnetic field. The paramag
netic effect is observed only in the presence of an external fie.ld : When the field is
removed, ind ividual moh:cular moments are randomized by thermal motion and the
bulk sample has no overall moment. When a field is prese.n t, there is competition
between the thermal tendency toward randomness and the field' s capacity to force
alignmenL
paramagnetic effects decrease in magnitude as the temperature is increased.
When any substance is placed 10 a magnetic field. the field produced wilhin the
sample will either be greater than or less than the applied field. dependin& on whether
the material is paramagnetic or diarnacnetic. The difference between the two (tJ{) can
be expressed as
llH = 8-H0
(11.31)
where 8 is the induced field inside the sample and Ho is the free-field volue.llH will be
negative (8 < HrJ ror a diamagnetic substance and positive (8 > HJ for one that is
paramagnetic. More commonly the difference between the applied field and that
induced in the sample is expressed in terms of/, the inunsity Q{ magnetization, which
is the magnetic moment per unit vOlume:
4'7TI
8 - H0
(11.32)
Because both 8 and I will tend to be proportional to an extemnl field, dividing

Eq. 11 .32 by H0 yields ratios (/IH0 and 8/H0) that will be essentially constant for a
given substance. The term 8/H0 , called the magnetic permeability. is a ratio of the
density of the magnetic force lines in the presence of the sample to the same density
with no sample: for a vacuum this ratio will be equal to I. The term IIH0 is the
magnetic susceptibility pt!r unit volume (K}, which expresses the degree to which a
material is subject to magnetiz:uion:
4TrK "'
8 /Ho- I
(11.33)
The value of " will be neaative for a diamagnetic substance and positive for one that is
paramagnetic.
The quantity that is most frequenlly obtained from experimental measurements of
magnetism is the
(or mass) susceptibility, X It is related to the volume
susceptibility through the density, d:
X - K/d
(11.34)
Magnetic
of Complexes
461
By multiplying the specific susceptibility of a compound by its molecular weight. we

can obtain the molar SIISceptihi/ily, XM:
(11.35)
XM = x MW
A number of methods exist for laboratory measurement of

tibilities.6t Two that are very common and quite similar to each other are the Gouy
and Faraday methods. Both techniques are based on the determination of the force
exerted on a sample by an inhomogeneous magnetic field and both of them involve
measuring the weight of a substance in the presence and absence of the field. The
Faraday method has two distinct advantages over the Gouy method . The first pertains
to sample size: The Faraday methocJ requires several milligrams of material whereas
the Gouy technique requires approximately I gram . A second advantage of the
Faraday method is that it gives specific susceptibility direcUy. The Gouy experiment
yields volume susceptibility, which must in tum be converted to specific suscep
tibility. This conversion can be problematic because it requires an accurate value for
density. which can be difficult to obtain for solids because the value varies according
to how the material is packed.
The setup for a Faraday experiment is represented schematically in Fig. II.S4. If a
sample of mass m and specific susceptibility x is placed in a nonuniform field H that
has a gradient in the x direction ll>H/8x) the sample will experi'eace a force (/)along x
due to the gradient:
f-
lmxH0 )
(S::)
(IJ.36)
This force can be measured by weighing the sample both in the field and out of the
field. the difference between the two weights being equal to f Commonly the experiment is simplified by detennining the force exerted on a standard of known suscepFig. 1154 Schematic
diasram of Uj)puratus used
for the Faraday
delennination of masnetic
susceptibility. The !Wimple
is suspended between
magnet pOles that huve
been carefuUy shaped so
that the value of
is constant over the region
occupied by the sumplc.
For discussion
of various torque and induction methods, includins those employina the vibratins
sallljlle rn:lllfl<lometcr and the supcroonductins quantum intcrfercna:de icc (SQUID), sec Gertoch,
M.
anJ LigunJ.Field Analysis; Cambridac University: New York. 1983; O'ConnOI',
C. J . Prog. lnorg.
1982.29. 20}-283.
462
11 Coorclination Chemistry Bonding, Spectra, and Mngnetism
<x =
1
tibility, such as Hg[Co(SCN)J
16.44 >< ro-f> cm1 mol- ). If the same
field and grudient ure used for both the standard (s) and the unknown (11), it is not
necessary to know the precise value of either. Hence
__
m.tXs
...k_
m,;x,
(11.37)
Solving this equation for the susceptibility of the unknown gives

v
""
= f.tnsX.
(11.38)
f.M,
The molar susceptibility of the sample. XM can be obtained from x,. by applying
Eq. 11.3S.
Once an experimental value of XM has been obtained for a paramagnetic substance, it can be used to determine how many unpaired electrons there are per
molecule or ion. In order to translate the experimental result into the number of
unpaired spins. it must first be recognized that a measured susceptibility will include
contributions from both paramagnetism and diamagnetism in the sample. Even though
the Iauer will be small. it is not always valid to consider it negligible. The most
common procedure is to correct a measured susceptibility for the diamagnetic contribution. Compilations of data from susceptibility measurements on a number of diamagnetic materials make it possible to estimate the appropriate correction factors. The
diamagnetic susceptibility for a particular substance can be obtained as a sum of
contributions from its constituent units: atoms. ions, bonds, etc. (Table 11.24). The
basic assumption underlying such a procedure, namely, that the diamagnetism associated with an individual atom or other unit is independent of environment. has been
shown to be valid.
The next step is to connect the macroscopic susceptibility to individual molecular
moments and finally to the number of unpaired electrons. From classical theory, the
corrected or paramagnetic molar susceptibility is related to the permanent paramagnetic moment of a molecule. p.. by:
(11.39)
where N is Avogadro's number. R is the ideal

constant. T is the absolute
temperature. and p. is expressed in Bohr mugnetons IBM) (I BM = e/r/47r111). Solving
this expre:;sion for the magnetic moment gives
(11.40)
As we know, this paramagnetic moment originates in the spins and orbital motions of
the unpaired electrons in the substance. There are three possible modes of coupling
between these components: spin-spin. orbital-ortXtal, and spin-orbital. For some
complexes. particularly those of the lanthanides. we must consider all three types of
coupling. The theoretical paramagnetic moment for such a complex is given by
,...
g[J(J
(IJ.41)
1))1/l
where J is the total angular momentum quantum number and g is the

factor for the electron. defined as
g =
+ J(J +
I)
+ S(S + I) - UL +
2J(J + I)
I)
splitting
(11.42)
Mav.,tic rrapertiea of Campi.,...
Tobie 11.2A
-eptibiliti..
[" 10 (cp ...m) mol""11
u
Na
K+
Rb+
cs
NH;
Hgl+
Mr
z.,l+
Pbl+
eal
F-
-9. 1
-23..4
-14.9
Br-
-2l.S
-34.6
-50.6
-3S.O
-3S.7
-13.3
- 40.0
NO]
- IS.O
-32.0
- 10.4
ow
-1.0
Cl-
-6.8
00]
ao;
CN-
-s.o
Ncs-
sc:r-
463
- 18.9
- 30.2
-32.0
- 13.0
-)1.0
-12.0
-40.1
- 12.0
Neutral Atoms
H
c
N (ring)
N (open cbaln)
N (imide)
-2.93
-6.00
- 4.61
-S.51
0 (dher or alcohol)
0 (aldehyde or ketone)
p
As(V)
-2.11
- 4.61
- 1.73
-26.)
-4).0
As( Ill)
Sb(lll)
Br
I
Se
-20.9
-74.0
- 6.3
-20. 1
-30.6
-44.6
- IS.O
-2).0
s..m. eo- Ligands

- I)
- 18
H:zO ..
NH1
<;H
CH)cooH1NCH 2CH1 Nfi:!
- IS
-30
-46
ace.l ylacetonale
pyridine
bipyridyl
o-phe.nanthroline
-zs
-S2
-49
-lOS
- 128
Co..atitvlive c:an.ctiaM
s.s
c-c
N- N
C=C-C=C
CeaC
C in benzene ring
10.6
0.8
0.2A
Carlin, R. L.
S!lrincerVertoa: New YOfk, 1986; p 3.
C-N- R
C-CI
C-Br
1.8
8.2
3. 1
4. 1
The: inner c:ore diamaanctism or the firsHOw tnnaition metals c:an be tAken as
approximatdy -IJ >< tO_. (cp units( mol- 1
The value of J depends on the total orbital angular momentum quantum number. L,
and the total spin angular momentum quantum number, S (Appendix C) . Some
calculated and experimental magnetic moments for lanthanide complexes arc shown in
Table II .2S.
For complexes in which spin-orbit coupling is nonexistent 01' ne&Jigible but spin
and orbital contributions arc both sisnificant, the predicted expression fOI' p. is
p. = [4S(S
I)
+ L(L +
l))tn
(11.43)
Equation 11 .43 describes a condition that is never fully rcaliz.ed in complexes because
the actual Ol'bilal contribution is always somewhat less than the ideal value. This
464
11 Coonfinalion Chemistry: Bonding, Spectra, and Mag.,etism
ToLle 11.25
Magnetic: .,.......m..
(ot 300 K) af..,....
C...trol
.,.,.,paunds al the
lallthanide metals
Ce3
J>r'+
Nd'+
Sm'
Eu'+
Sm1
Gd)+
Eu1+
Tb,.
nyJ+
Hol+
........
Er
Tm'
No. of/
electrons
I
Ground
Ifate
Compoo.nd
ZF
Ce1Ma1 (N<>,4 24H1 0

Pr2(SOJ3 8H1 0
,9/l
Hsn.
.l
6
6
7
7
8
9
10
II
12
13
1F
7 0
,Fo
Ssn.
assn.
1F
'
Hun
'l
J,yz
'R
1 6
F7n
Nd1(S0,.)3 8H20
Sm,(SOJ3 8H10
SmBr1
Gdz(SOJ3 8H 20
Eu02
Tbz(SO.>, 8H20
Oyz(SOJ 3 8Hz0
Ho1(SOJ3 8H20
& 1(50,.)3 8H20
Tmz(SOJ:, 8H10
Ybz(SOJ, 8H2 0
p.(.-pt)
BM
2.28
3.40
3.SO
I.S8
3.42
3.S7
7.91
7.91
9.SO
10.4
10.4
9.4
7.1
4.86
:.1
#'(calc)
3..58
3.62
1.6<
3.6J<
3.61<
7.94
7.94
9.72
I
I
10.63 1
10.60
9.S7
7.63
4.SO
Fl81i$, B. N. In
CtXKdlnoll<ln Cio<miJtry; Wdkinson, G.; Gillard, R. D.;
McC1e\'CI1y, J. A., l!ds.; Perpmon: New Yoli<. 1987: Vol. I, p 261 .
I(J(J + t)]"'.
<
where DOled.
Calculation inclu&lea ell"oclS of mbti.. Of around and hiaber enefJ)I turns.
occurs because the orbital anaular momentum Is reduced from what il would be in lhc
free melal ion by the presence or ligands. In the extreme case, where L is effectively
zero. the orbital contribution to the magnetic moment is said to be quenched. This is
the general situation in complexes having A orE ground states. which would include
octahedral d 3 d' (high spin). d' (high spin), tl' (low spin), d 1 (low spin), and d 1 cases.
Furthermore, when a complex involves a first-row transition element, even if the
ground state is T. the orbital conuibution eenerally may be ignored. For the L = 0
condition, Eq. 11 .43 reduces to
p. = (4S(S
+ I)Jm
= 2(S(S +
l))vz
(11.44)
which is known as the spin-only formula for magnetic moment . By recognizing that S
will be related to the number or unpaired electrons (n) by S = n/2, the expression may
be further simplified to
p. = [n(n
+ 2))112
(11.45)
A number of calculated and

maenetic moments for lim-row transition
melal complexes are given in Table II . 26. showing that the spin-only formula gives
results that are in reasonably good agreement.
As we know. a number or transition metal ions form both high and low spin
complexes. and we have now seen that magnetic susceptibility measurements allow us
to experimenlally distinguish one from the other. Within ligand field theory, these two
spin configurations in octahedral
are explained in terms of relative magnitudes of 6., and pairinc energy (P): We assoc ia te hich spin complexes with the
condition 6., P. For complexes in which the
energy difference between 6, and Pis relatively small. an intermediate field situation,
it is possible for the two spin states to coexist in equilibrium with each other. Consider
the Fe2 + ion. At the two extremes, it forms high spin paramagnetic (Fe(H20))1 + (S ..
21 and low spin diamapetic [Fe(CN>.f- (S .. 0). The Tanabe-sugano diagram
Mognet;c Propemes of c.,...plexes
465
Tobie 11.26
Magnetic properties ol 50flle c-plexes ol the lint-.- tronsirion .,....
'...
Cenfrol
metal
TiJ+
v
v,.
,vz+
cr'
t Mno.
cr
Mn2
Fe)+
Fe2
Co'
Co2+
I'Ni,.
Nil+
,cu,..
High spin compl-s
No. of
No. of tl
efec:trons
.....,.,;r.d
electrons
,. lx1
,. (cole)
BM
BM
I
I
I
I
2
3
3
3
4
4
2
3
3
3
4
4
5
5
4
4
3
3
2
1.73
1.68-1.78
2.75-2.8.5
3.80-3.90
3.70-3.90
3.8-4.0
4.1,-4.90
4.90-5.00
5.6l-6.10
5.70-6.0
S.I0-5.10
1.73
1.73
2.83
3.88
3.88
3.88
4.90
4.90
5.92
5.92
4.90
4.90
3.88
3.88
2.83
1.73
5
6
6
7
7
8
9
!. 8urJer, K. Ccort!Dtolion Clwmisrry:

_! Spin-only
.4.3()..5.20
2.B0-3.50
1.70-2.20
-No. of
unpoired
low spin COflll'les
,. ,.,..,.,
,. [cole)
BM
BM
3.20-3 ..30
3.18
1.80-2.10
2.()..2.5
2.83
2.83
1.73
1.73
0
0
I
1.8
1.73
1.&-2.0
1.73
2
2
I
I
Mrdtods; Bwcrwonb: London, IJ7l.
vallle.
pertaining to these d" complexes (Appendix 0) shows that near the crossover point
between weak and strong fields the diiJerei'ICle in energy between the spin-free <'T:!)
and spin-paired (1A 1_.) ground states becomes very small (Fig. I I.S5). Within this
region, it is reasonable to expect that both spin states may be present simultaneously
and that the degree to which each is represented will depend on the temperature (ll.n P = kT). A complex illustratina these eiJects is [Fe(phen)1(NCShl A plot of its
magnetic moment against temperature appears in Fis. II .S6. At high temperatures a
moment consistent with four unpaired electrons is observed, but as the temperature is
Fig. 11.55 Vanution in
enersies or the 'Tz.. and
'A ' terms with increasing
A.. for d" octahedral
complexes. At weak fields
(1\i&h spin complexes) the
around term is 'Tz.., while
ut suorc 1\elds (low spin
cocnplexesl it is 'A Note
tbut in the rqion
immediate.ly on each side of
the spin crossover point,
the energy ditretQ>Ce
betMen the two terms Is
A--
small; thus hi&h and low

spin complexes may
coexist.
470
11 Coordinolion Chemistry: Bondi.,g, Spectro, o,.d Mog,.etislll
11. 19 Why is a solution d coppertll) sulfate blue'!

which would beexpec.ted to have the
11.20 lh>ne ICUt...J' solutioo is blueun&l

higher vulue of A..?
11 .21 Consider the following elect ronic
complexes hlma dimethylacetamidel:
Complrx
[Ni(H:()l.f
(NiCNH1l..f
[Ni(OSMe,>.J'
[Ni(dllllllr.f
".:
8500
t0.7.5()
1S16
Delennine npproprinte vnlues
15.400
17.500
12.970
12.7311
frequencies (in cm- 1) for a series of nicket(ll)
"'
26.000
28.200
24.038
23,809
and 8' ror these complexes.
11.22 The follo wing absorplion bands are found ;, the spectrum or [CrtCNIJ'-; :!64 nm <cbarse
t111osfer). J 10 nm. and 378 nm. Determine the values d A., 1111d 8' .
11.23 When visible light passes through a solution d nickd(ll 1sul(ure. a green solution results.
Wllal are the spin aUowed tnnsi rions respons;ble
this color'? Would you expect a
Jllhn-Tdler wstonion for this complex ?
ror
11.24 Chromium(ll) ftooride :lf1d manpllCSeC III lluoride both have a central metal ;o., surrounded by six fiuoride lis:Jnds. The Mn-F bond lencths are equidistnn1. bu1 four d the
Cr- F distances are
and two are shon. Provide an expl.lnation.
11.25 If u molecule having n center d symmetry undergoes a John-Teber distortion, the cen1er
or symmetry must be maintuino:d. and this is rhe cue when octahe.Jru UOOCfl:O ta111gonul
distortions. Can you think or uny o1her distortion dan ocl.llhedral complex that would be
conslslent with this principle?
11.26 Both FeF, nnd K, [CoF.J contain six-coordinote hi;h spin metal ions. Tbe electronic
spectrum or the former shows ub$orptions ur 6990 and 10.660 em - . while the Iauer has
absorptions or 10,200 and 14.SOO em- . For which complex is A.. lArgest? Why? How
many multiplicity allowed elc:erronic
would you expe.:1 for these complexe.<?
How """ you account fo r the presence o f rwo
in each
11.21 The ligand-tomcral cll>lrae
ICo Br.J < )CoCI.J' . Expkoin.
in energy in the series: JCoi.J-
<
11.211 Expluin the: following (from Lever. A. 8 . P. J. Ch<m. <111<'. 1914, Sf. Clt2-CliM:
The ""hydrous
nor stable.
CuCI1
CuBr, a rc11rccn and black. respectively. while Cut,
b. The NCS- ;o., is u coed colorimetric rcua:cnr ror Fe Ill!.

Complexes in which awo met:lls of diCTcn:nt oxidation state are c lo.se IO&Cther arc
freqoenlly highly colored .
d. Mlllly complexes exhibirina churae trunsfer bonds in the visible region are unsroblc in
sunlight.
11.29 From the reacr;o., ol NiBr, and Ph1ErP. it is possible ro isolate

crystals of
JN i(Ph,EtPI,Br,), which lwve a
momerc d 3.20 Bohr maaneaons, and red
crystals d [NiiPh,EtP):,Bc,), which have a
moment d zero. When either of
thc:se is dil;solved in dichloromerhane ar <40
the resultinc solution h:as a maanetic
moment ol 2.f/J BM. Suacsr SJructures for I he arccn and red aystals ond offer an
expklnalion for the solution rmcneric moment. (See l.:IMar. C . N.: Shennan, E. 0 . J.
Am. Clwm. SOC'. 1970. 92, 269 1.
c.
II .JO Calculate the magnetic momeru of Oy,CS04!.1 8H:().
Pro!>lems
4 71
II.JI Show thai the sround srnae lenn of Er' is 4 /om Whnl mliiJlCtic moment would YQJ
expect for Er::(S04 !,8H,O'!
11.32 The complexes ( MntH,Ot,J'. (FeiH!Ol,J'. (MnO.J'- , nnd (Fe04 ) - all have mill!
netic moments of nearly S.9:! BM. What does this tell you about rhe geometric and
electronic structures ofrhese complexes? Why is the spin-only fOrmula so precise in these
cases?
ll.JJ One means of determining the magnetic suscepcibility of a transition mcral complex. rhe
Evnns mer hod. urilile. NMR. As an illustration of the procedure. considu the following
experiment utilizing a 6().MHz spectrometer. A
rube is filled with an aqueous
solution oonsisaing of 8.0 l11ll mL-o of CuSO. in 2% r-buryl alcohol . The capillary tube is
sealed and pL1ced in un NMR rube rhar also conraina a 2"/.tbulyl alcohol solution with no
OJS04 The volume susceptibilities
the rwo 1;0lurions dilfer und a.s result rhe r-buryl
sroup shows n d ift"ercnt pr01on chemical shifl in each. For this panic:ular experiment. the
chemical shift olrhe r-buryiQtoup in the copper solution is 8.6 Hz upfield from that in the
noncopper solution ar 310 K . Use the!<e dura and help from Loligcr, J.: Scheffold. R. J.
EJuc:. 1972. 49. 646-M7. to determine the lliii8RCiic moment uf Cu$04 How does
the value you obtain compare to rhar expected from the spin-only formula?
or
11.34 Explain the followin& expetimenral results : Ar ambient remperawre a 0. 192-. sample or
FeiHB< I-pyrarotyl>,h wef&hs the same in a magnetic: field as ir cloes our o r rhe field 110
three signifieaol fiaure:u. However. in on identic,l maQnetic
111 449 K, a 0.192-t:
sample
the same marerilll p ins O.OIS cover irs our-of-&ld wdghr. (See Hutchinson.
8 . : Hance. R. L.: HnnJecree. E. L. : Rus.eU S. A. J. Cl,m. EJuc. 1980. j7, 830-831.1
or
11.35 When ethylenediamine os udded 10 a

on of coboktlll chloride hexahydr.ate in concentrated hydrochloric: acid, o llluc
solid is ubtoined in
Analysis
this
compound shows that ir conlcins 14. 111% N. 12. 13% C. S.O'r- ' H. and !03.70'1. Cl. The
cfrecrive
moment is
as 4.11 BM. The hlue complex
in water oo
give a pink solution. the conductivity ur which is lSSl ohm - o em: mol - 1 at :!1 c. The
visible spectrum ola dmsosolurion ofrhe complex has bands cc:nrered ar J2 17. S6l0. nnd
IS. ISO em - (mubr absorptivity S'JO mot - L c:m- 1). bur for a w..rer solution. the absorptionsoccurati!OOO. -t6.001hnd
- lmol- 1 Lcm- 11.
In a rirmrion with sodium hydroxide. eac h mole of the complex ncurrolizes four moles
base. Determine the formula and structure o r the comrlex. Account for all reactions :uxl
observations.
or
""''''"red
or
11.36 Addition ufTiChroan nqueous solurion o fu reo followed byallditionofKII!'lvcdecpblue

crystals o r a complex conruininglilanium. urea. and iucline. The visiblo: spectrum of I he
materiol showed one ahsorplion ;ol II!.IMMI em - and irs mugnetic moment wus determined
robe I. 76 BM. When 1.000 g or the compeund was dc:comrosed ur high rempertures in an
oxygen ormospho:ro. oil ticHnds volorililed and O. l!ll g or TiO, formed. Deduce rhe
formula and nrucrurc of 1hc complex . Oo you think urea or water lies higher in the
spectrochemical series'! How might you deoennine whether urea is bound to titanium
through oxygen or rhrouJIIl nirrq:en?
11.37 In the solid stare, Cocpy):CI: is violet and has a magnetic moment o(S.S BM. but aCH:O:
solution olthis oompound is blue und has o magnetic: moment or 4.42 BM. In contrast,
Co(py),Br, is blue in both rhe solid stare and in u
solution and has a ITUign<lic
moment of 4.11 BM in both (()f'Jm .
these observorions. Predict the colors and
magnetic ITI)menrs ol
and Coepyl: l1
II.J8 lr has been lcbown alleust since the IStb century thnt bhle &lass could be obtained by
includinc CObalt{ I I) in the forrrubrion.
from its he;aury.
type of class is useful
for absorbing sodium e mission thereby allowi"41 one 10 ob5erve the char:ICicrisrk !lame
lest for poll>Ssium in the prc5ence of sodium. Explain. Low alkali bor.>le gla.sses conrait>inc coball(ll) do nor pve goud cobalt blue-they rend 10 be pinlc . Adclirion o f some NaO
to the C)ass cleepcns rhe blue c:olor. Why? !Paul. A.
of G#os.sh, 2nd ed.;
Chapman and Hall : London. 1990: pp 32Jif.)
C h
a p
e r
12
Structure
T he previous chapter described the bonding principles responsible for the energetics
and structure or coordination compounds. In this chapter the resulting structures will
be examined in more detail with particular regard to the existence of various coordination numbers and molecular structures, and the effect of these structures on their
chemical and physical properties.
The coordination numbers of metal ions ranee from I, as in ion pairs such as
Naa- in the vapor phase. to 12 in some mixed metal oxides. The lower limit, I, is
barely within the realm of coordination chemistry, since the Na ca- ion pair would
not normally be considered a coordination compound, and there are few other examples. Likewise, the upper limit of 12 is nOt particularly important since it is rarely
encountered in discrete molecules, and the treatment of solid crystal lattices such as
hexagonal BaTi01 and perovskite' as coordination compounds is not done frequently.
The lowest and highest coordina.tion numbers found in "typical" coordination compounds are 2 and 9 with the intermediate number 6 bein& the most important.
We have seen in Chapter 4 that the coordination number of ions in lallices is
related lo the ratio of the radii of the ions. The same ceneral principles apply to
coordination compounds, especially when a single coordination number, such as 4.
has two common geomellies-telrnhedral and square planar. An extended list of
radius ratios is given in Table 12. 1.
Coordination
Number 1
As mentioned above, ion pairs in the flDS phase may be considered as

of
coordination number 1. There are a few other examples known . For instance, the aryl
radical derived from the highly sterically hindered 1,3,S-triphenylbenzene, fonns oneto-one2 orpnometallic compounds or the type CuC6H1 (C6 H5) 3 and
as shown in the margin.
1
Nelle. howc:vcr,lhrll some o( the properues o( melal ions in 1hcsc systems can be described in lenns
of coordi""l.ion chcmislry. Sec
7.
R.: Strahle. J.
C/wm. Int. EA. &11. ttu,17, 436. Nole tllat whel we: oflen naively
write as ""UCH1 ." '"Li(;Ji,," '"KCH 1; and "C..CH," arc ollen considerably """"complex:
tliOi,Ju (hcluuncric molecules in hy4roca1t>on solvenl$, leln>menc molecules in THF and the
solid). K CH)(io<Ocsolidl. and (CuCH,J, lbridaed polymetic: solidi. See Elschcnbroiclr, C.; Salzu.
A. Organomdaliu, 2lld cd.: VCH: Weinhcim. Cc:nnany. 1992: pp 20-21.
Coordination Number 2
473
Tabl.12.1
C.N.
4
6
6
7
0.225
Tetr.lhedron
Octahedron/square plane
Tri&onol prism
Capped octahedron
Square antiprism
Dodecahedron (bisdisphenoid)
Cube
Tricappcd tri&onal prism
icosahedron
Cuboctahedron
0.414
0 ..528
0.592
0.645
0.668
0.732
9
12
12
0.732
0.902
1.000
Coordination
Number2
Mnmu.,.
roclius rafio
Few complex ions are known with a COOfdination number of 2. They are gcocrally
limited to the + I ions of the Group 18 (II) metals and the closely related Hg(IJ)
species
Examples arc [Cu(NH.YJI+. [Ac(NH1 ) 2l. [CuCI2J- . [AgCI!J- .
[Ag(CNI:!I-. (Au(CN)zr, and [Hg(CN>zJ. Even these may react with
additional lipnds to form higher-coordinate complexes such ns:
[AI(NHj)v+
[HI(CNhl
+ 2NH3
+ 2CW -
----+ (Ag(NH 3)J+
[Hc{CN)j-
{12.1}
(12.2)
The low stability or two-<:oordinate complexes with respect to other possible

tures is well iUustrated by the cyano complexes. Although s ilver(l) and gold(!) form
discrete bis(cyano) complexes. solid KCu(CN)z possesses a chain structure in which
the coordination number of the copper{!) is 3.
If the licand is sterically hindered s ufficiently, such as (N(SiMey2 ) - ,
[N(SiMePh2J2
and
two-coordinate complexes may
also be fo rmed by ions such as Mn!+, Fe2+, Co +, and Nf2+. 1 The last two ligands
have the advantage that t he boryl sroup draws off one of the lone pairs on the nitrogen
through N_.B dative.,- bonding and reduces the tendency of the nitrogen to bridge
and form dimeric complexes.
The geometry of coordination number 2 would be expected to be linear, either
from the point or view or simple electrostatics or from the use or sp hybrids by the
metal (but there are exceptions; see Chapter6). If the (n - l)dorbitals of the metal are
sufficiently close in energy to the ns and np orbitals, the d' orbital can enter into this
hybridization to remove electron density from the region of the ligands. The tendency
for this to occur will be in the order Hg Au > Ai > Cu because of relativistic
effects4 (see Chapter I g). This, in tum, may be partially responsible for the increased
softness or Au()) and Hl(ll) (see Chapter 9).
r.
> Mea
8.
Xyl s c.H,Me1 . See Chea, H.; Banleu, R. A.: Olmstacl, M. M.; Power, P. P.;
J. Am. CNm. S. 1990. 111, 104&-IOS.S. Power. P. P. Commtnts lfi<Ht(. C/trm. tm.
:nl references cited therein.
Sebwerdtfegcr. P.; Boyd. P. D. W.; Blm:ll, A. K.: Rcbinson, W. T.; Taylor. M. J. /nnrg. Chlm.
1990. 19. JS9J.-l607.
474
12 Coordination Chemistry: Structu,..
Coordination
Number 35
This is a rare coordination number. Many compounds which might appear to be threecoordinate as judsed from their stoichiometry are found upon examination to have
higher coordination numbers. Examples are CsCuCI1 (infinite single chains.
-CI-CuCJ..-cl-, C .N. 4 at 228 and 236 pm; two more a - from adjacent
segments at i18 pm: note the operation of the Jahn- Teller elfect), KCuCI1 (infinite
C .N . 6. distorted octahedron), and NH4 CdCI1
double chains,
(infinite double chains. C.N . = 6, undistorted).
The KCu(CN), chain described ubove (- CN- Cu(CN)- (CN)-Cu(CN)-) is
an example or
three-coordination. Some other examples of three-coordination
that have been verified by X-ray
are tris(lrimeth ylphosphine sulfide)copper(l)
perchlorate, [Cu(SPMe1) 1 )[CI04 ) (Fig. 12. 1a), t)'do-triS(chloro-jJ.trimethylphosphine
sulfide)copper(l) (Fis . 12. 1b), the tris(t-butyllhiolato)mercurate(ll) anion7 (Fig. 12. 1c),
the triiodomercurate{ll) anion. [Hsl1 )-, and tris(triphe.n ylphosphine)platinumiO).
[(Ph,P)1 Ptj. In aJI examples the seometry a pproximates an equilateral triangle with the
metaJ atom atlhe center of the plane as expected for
hybridization. Some d orbitaJ
pasticipation can be expected as in the case of linear hybrids. since a trisonal stP
hybrid is aJso possible. C.N. 3 is also favored by steric considerations over the
more common C. N. e 4, and because electronic factors do not favor it. the former
must be dominant.
A few complexes are known in which the geometry is planar but not equilateral.
One ansJe may be much sreater than I ZOO (Tshaped. F'IJ. 12.1dl or much less than
IZOO (Y-shaped, Fig. 12.1e). Just as the bond anaJes are no longer equal, t.h e bond
lengths are no longer equal (see Problem 12.29).H
Coordination
Number 49
This is the first coordination number to be discussed that has an importam place in
coordination chemistry. It is also the first for which i!OOmerism is to be expected. The
structures formed with coordination number 4 can be conveniently divided imo
lttruhedral and square planar forms although intermediate and distorted xtructures
are common.
Tetrahedral
Complexes
Tetruhedr.ll complexes are favored by steric requirements. either simple ckclrost:tic

repulsions of charged ligands or van der Waals repulsions of large ones. A valence
bond (VB) point of view ascribes tecrahedral structures to .fp' hybridization. From :1
crystal lield (CF) or molecular orbital IMO) viewpoinl we have xeen that . in general .
telrahedral structures ore not stabilized by large LFSE.
complexes are
thus favored by large lig;tnds like Cl-, Br- , and 1- and small
ions of three types:
' Eller. P. G.: Br:.clley, 0 . C. ; Hurllthouse. M. B.; Mcrk. 0 . W. CtH>rJ.

Rn. 1m. 24. t-95.
Toethd. J. A.: Hc.t ey.
AToerhof. J . A.: Slllliclc, J . K.: Meek. 0 . W . /""'ll Clttm. t91J, 11,
A. T.; Meek. 0 . W. '""'ll
1914. /J. 230S- 2$09. Eller. P. G.: Corlietcl. P. W. R. Cbtm.
Commun. 191t. IOS-106, Fem. R. H.: Oldham, J. W. H.; rlll11ips. 0 . C. NIIIMN' tii6J. /91!. JKI-382..
Albano. V.; Bcltcn. P. L.; Sonurin. V.
Co,..n. 1966.
> This anion h:o been ptopo.cd as a mocltt COfl1llOUIId f the reccpt <ile in a mercuric bio.<ensor
(Watton.. S. P.: WtW>t, J. G.: MacDonnell F. M.: Bryson. J. W.: Sabat. M.; O'Hulloran. T. V.
J. Am. Ch1m. Soc. 1990, 112. 2824-211161. S Olapto" 19.
For example. sa: Munalwta. M.; MaekaWll. M.: Kitapwa. S .: Motsooyam.o., S .: M:I<Uda. H.
Cittm. 19119. 16. 4301l-4l02. ond references therein.
9
Favu. M. C.: Kcpen. 0 . L. 1'-. lnCKJt. Chtm. 1980,27. ):!S-46).
Coordination Number 4
11
(b)
475
IC)
(cl
Fig. 12.1
complexes: lal Cu[SP!Me,))l: (b) (CU(SP(CH, J,lCI),: lcl (Ha(SBu'h)- : (d)

(C.H, CH%N(CH%CH%C,H.N),CuJ : (el
.. Carbon atoms ure IJniTIIII'I(ed and
aroms
have been omillcd. (From Eller. P. G.: Corfield. P. W. R. Chtm. CommNn. 1971. 10$-106. T'tethof. J. A. : Slalick. J. K .:
Meek. D. W. lnoR Chtm. 1973, 12. 1171>-1174. Tiethof. J . A. : Hetey. A. T.; Meek. 0. W. ftot:Jrfl . Clrrm. 1974. /J.
7J0$-2S09. Warton, S. P. ; Wrishl. J. G. : MacDonnel, F. M.: Bryson, J. W.: Sabol. M. ; O'Halloran , T. V. J. Am. Chrm.
SM. 1990, 111.2824-2826. Bbckbum, N . J.: Karlin. K. 0 . : COIIcannon. M.: Hayes. J. C.: Guhneh, Y.; Zllbiera, J. Cikm.
Cummun. 11184. 9)9-940. Munakara. M.: Maekawa. M . : Kitagawa. S.: Matsuyuma. S .: Mosuda. H . '""'R Chtm. 1989. 1/J,
4300-lJOl. ReprodUced with pcrmssion.)
(I) those with a noble cas confisuration such as Be:+ (ns"l: (2) those with a pseudonoble gas configuration (n - l)d 11lll'np11 , such as zn: ond Gal+: and (3) those
transition metal ions which do not
favor other structures by virtue of the
LFSE, such Co2 , d 1
Tetrahedral complexes do not exhibit geometricnl isomerism. However, they are

potentially chiral just as is tetrahedral carbon. The simple form of opticnl isomerism
exhibited by most organic enantiomers, namely four different substituents. is rarely
observed because substituents in tetralledral complexes are usually too labile to for the
complex to be resolved, i.e., they rocemi:te rapidly. However. an interesting series of
cyclopentadienyliron phosphine carbonyl compounds (see Chapter IS for further
oo LDblll' rd'en nclto thennodMmic sllbiliry per se bul. rather. to the- of subslitUiion by o1her
lipnds. In addition to bond
the ecceuibiliry cia suitable mechanism also tolllributc:s ro
rhc iner1nes1 or lllbiity
Olapter ll). l..atlile ia one cit.h ose words
lion of wtric:h American chemists scan unable to QIRC 1410'1 Some l'olow llle dic!ionary and rhyme
it man oc less with iU antonym.
Others rhyme it with Mobilt. and a thin! aroup shows an
EnaJish or Australian bent and rhymes io with
476
12 Coardlnation Chemiotry: Structure
Ill
o::::C
'
CH,
{a)
(b)
Fig. 12.2 (a) Line drawina or an acelyl(c:arbonyl)(cycloperudlenyl)(phosphincliron complexJ. D.; Bernal, I. J.
(b) Stereoview or the same molecule. [From Korp,
1981, 22(), JSS-364. Reproduced with permission. )
discussion of organometallic compounds) has been synthesized and characterized. A

line drawing and stereoview of one of these is shown in f'q:. 12.2. Note that the large
c,H, ring forces the other ligands back until the bond an&les are essentially 90" rather
than 109!0 Indeed an argument could be made for considering the complex to be eightcoordinate, thoush lillie is gained by such a view. The chirality of the molecule is the
important feature to be noted.
A second form of optical isomerism analosous to that shown by organic
spirocyclic compounds has been demonstrated. Any molecule will be optically active
if it is not superimposable on its mirror image. The two enantiomers of bis(benzoylaceton.ato)beryllium arc ilustrated in Fig. 12.3. In order for the complex to be
chiral, the chelating ligand must be unsymmetric (no/ necessarily asymmetric or
chiral, itself); [Be(acachl is not chiral.
II Brunner. H. Adv.
C/wm. t980, /8, ISI- 206. Korp, J. 0 .; 8emaJ. I . J. Drltmomrl.
CMm. lfll, 220. JSJ-364. J.
C/wm. tfll,110 (entire islue devOicd to ''Otpnomelalic
Cocrlpounds and Oplieal Adivily," cditecl by H. Brumer). Saun-Uamas, 1.; Dallon, D. M.; Arif,
A. M.; Gladysz. J . A. Ortunomnullia 1991. //, 683-693.
Coorcli110tiae Nu111her 4
Fig. 12.3 Enantiomen
Squar e Planar
Compl
o(
4n
bis(bmzoylacelonlllolberyllium.
Square planar complexes are less favored sterically than tetrahedral complexes (see
Table 12.1) and so are prohibitively aowded by large lipnds. On the other hand, if the
ligands are smaU enough to form a square planar complex, an octahedral complex with
two additional a bonds can usually form with little or no additional steric repulsion.
Square planar complexes are thus formed by only a few mellll ions. The best known
are the d' species such as Ni2+.
Pl2+, and A.; (Chapter II). There are also
complexes of Cu1 (d"). Co2 (d7 ),
and even CoJ (cf) that are square
planar, but suc.h complexes are not common.IZ The prerequisite for stability of these
square planar complexes is the Jlf"C:Sence of non bulky, strong field ligands which w
bond sufficiently well to compensate for the energy " lost" through four- rather than
six-coordination. For Nr, for example, the cyanide ion forms a square planar
complex, whereas ammonia and water form six-coordinate octahedral species, and
chloride, bromide, and iodide form tetrahedral complexes. For the heavier metals the
steric requirements are relaxed and the effective field strength of all ligands is in
creased. Under these conditions, even the tetrachloropalladate(H), tetrachloreplati
nate(Il), and tetrachlo roaurate( UI) anions are low spin square planar.
One unexpected square planar complex (Cd(0Ar)z(lhf)1J(Fig. 12.4) has recently
been reported.IJ It is the first example in this geometry for d to Cd1 . Inasmuch as a
closely related complelf. of the smaller zinc ion. (Zn(OAr' )z(thfh l. has distorted
tetrahedral geometry , 14 simple steric factors cannot account for the pseudo-Dv. sym
me try of the cadmium complex, thouch to be sure, the s teric relaxation of the larger
metal atom and the perpendicular planes of the thf and phenoxide rings are nicely
accommodated by it. Furthermore, octahedralseometry would not be unusual in ad 10
cr
HetmeS, A. R. : Morris. R. J.; Girdami, Ci. S.

191S, 7, 2372-2379. Brewer, J. C.;
Collins, T. J.; Smith, M. R. : &ntarsicro, 8 . 0 . J. Am. Chnrt. Soc. 191S, 110,
11 Cod, S. C. :
M. Y.: Bullto, W. E. J. Am. Chrm. S. 1990,//2, 6724-672S. -OAr a 2.6diofb:llylph<noxide. thf telnlllydtofo.nn. Anottou
in which this aecwno:u y occun unex
pcctcdly is (R,P(OINR'bNi (R Bu'; R' filii. which liAS been shown to be squore . .rw and
a combination 1101 predicted for
metal ion . (Fr&nmd. T.: Pttcn. W.; wdcrlich. H.; KuchCft. W. ""'""' Chrm. Int. Ell. log/. lfn, Jl, 612-6 111.
micrOS)'IIIIIletrl' ot the zinc w;u, an Ar'O.Zti-OAr'
o( 122" and a lhfZn-thf anaJe ofW.
- oAr' 2,4,6-(ri+blllylcl!KnoJtide.
12
c.,.
478
12 c-rdinotion O.emiotry: Strvdun
Fig. 12.4 ORTEP of

[Cd(OArh(lhflt). Hydrosen
atoms have been omined
for clurity, 'The Cd arom

resides on a cry$lalk>-
.,.aphic inver$ion cmler.

[From Goel, S.C.; Chiang.
M. Y.; Buhro, W. E. J .
Ant. Ch nt. SOC'. 1990, Ill,
with permission.)
species, but the 2,6-di-t-butyl groups may prevent coordinatio n of a fifth and sillth
ligand . F rom an e lectronic viewpoint, it may be that the stronger cadmium-phenoxide
bonds dominate the bonding picture, leaving the wealdy basic thf molecule! to bind
as best they can." If so, this would be an example of Bent's rule (the muimizal.ion
of s character towards the strongest bonding ligand) acring in a complex ion. See Problem 12.38.
Square planar complexes of the formula
may exhibit cis-trans isomerism:
; .,.....Pt, ;
CI-------NH 1
cis-diamminedicbloroplatinum (II)
Pt
H,NC-'-..
tr.......tiammincdichloroplatimun(tt)
If such complexes a re neutral molecu les as in the above example. they may be readily
d istinguished (and often separated as wet I) by the presence of a dipole moment (I-') in
the cis isomer but none in the t rans isomer. O nly in the unlikely event that the M-A
and M-8 bond moments were identical could the cis isomer have a zero dipole
moment .
Square planar complexes rarely show optical isomerism. The plane formed by the
four ligating atoms and the metal ion will ordinarily be a mirror plane and pre vent the
possibility of chirality. An unusual exception to this aeneral rule was used in an
ingenious experiment to prove that platinum( II) and palladium( II) complexes were not
tetrahedral." CarefuOy designed complexes (Fie. 12.Sa) with square planar structures
have no improper axes of rotation and hence are c hiral. If these complexes were
tetrahedral (Fis. 12.Sb), there would be a mirror plane (defined by the metal and two
nitrogen atoms from isobutylenediamine) reflecting the phenylsroups, methyl groups,
etc. Inasmuch as optical activity is found experimentally, these complexes cannot be
tetrahedral and, barring some u nusual aeometry, must be square planar.
" Haalancl, A. Anr<'"' Clwm. Int. EJ. Engl. ""28 992-1007. Sec allo Foocnote ll.
'"Mils. W. H.; Qujd, T . H. H. J. Clwnt. Soc. 1935, 819-346, LidsiOIIC, A. G.: Mils. W. H.
J. Chmr. Soc. 1939. 17*t7S9.
Numloer 5
479
Fig. 12.5 Possible

slnlcturea of
stilbenediamine)
(isobutylenediamine)
palludium(ll) and
plutinum(ll)
(I)
planar s.IJ\Iclure, oplicaly
uctive; (b) tetrahedral
suuc:ture, oplic:aUy inocrive.
fl,l
(b)
Coordination
Number 517
ln lhe past a
number ofS was considered almost as rare as a coordinatioo
number of J . Again, many of !he compounds which might nppear to be live-coordinate
on the basis of stoichiometry are found upon cJose examination to have other coordination numbers. Thus Cs3CoO, and (NH.J3 ZnCt, contain discrete tetrnhedrlll
anions and Cree chloride ions. Thallium nuoro:lluminale,
is composed of infinite chains, -F-AIF4 -F, in which the coordination number of !he
aluminum is 6. The
of cobalt(JI) chloride and diethylenelriamine,
H 2NCH 2CH2NHCH 2CH2NH2, of empirical formula [CoCI 2dien) is not a five-coordinate molecule but a salt, [Co{dien),J[CoCI4 ), containing octahedral cations and
tetmhedral anions.
If electrostatic forces were the ooly forces operaling In bonding, five-coordinate
compounds would always disproportiooate into four- and six-coordinate species (as
does the "Co(dien)CI 2" complex above). Since covalent bond ina is obviously of great
importance in coordination compounds, it is possible to have stable five-coordinate
complexes. but it is true that there is a delicate balance of forces in these complexes,
and their stability with respect to other possible structures is not areat. For example,
the compound [Ni(PNP)X2] (where PNP - (C.,H,),PCH2CH 2NRCH 2CH 2P(C6 H_,):z)
is a true live-coordinate species. bu t on warrnina slightly it converts to
[Ni(PNP)X)z[NiXJ, which contains both square planar and tetrahedral species. AnOlher example is !he pair of compounds of empirical formula MX2(Et4dien) where
M =Co or Ni, and E..dien = EtzNCH 2CH1NHCH1 CH 2NEt1 . The cobalt complex
is live-coordinate, but the correspooding nickel compound is four-coordinate,
s.
n For reviews ol coonlinalion numbtt see Holmes. R . R. l'rog . '""'' ChD>t. 1914. 12. 119-235;
Kepcrt. 0 . L In Comprrhnulvr CcordJMiiDtr
Wilkinson. G.; GIMord, R. 0 .; McCicvaty. J. A. E<b.; J'apmoo: Oxforcl. 198'1; Vol. I. pp 19-4.
480
12 Coo<clinatloc: Chemistry: Structure
Umiting Geometries:
Trigonal Bipyramidal
and Square
Pyramidal
Although five-coordinate compounds are still less common than those of either coordination number 4 or 6, recently there has been considerable interest in them, and the
number of compounds with known structures has increased rapidly. The complexes
can be described as "regular" or "distorted" triaonal bipyramidal (TBP; Fig. 12.6), .
"regular" or "distorted" square pyramidal (SP; Fil;. 12.7), or as "highly distorted
structures," i.e., somethins between TBP and SP. As we have seen, however. every
intermediate structure between "perfectly TBP" and "perfectly SP" is possible
(Chapter 6), and it serves little purpose to try to fit them into neat "pige.onhole.s." The
differences between the various structures are oflen sliaht and the energy barriers
tending to prevent interconversion are also small.
or particular interest in regard to the delicate balance between the forces
favoring TBP versus SP structures are two pentocyanonickelate(ll) sal ts with different but very similar cations. Tris( I ,3-diaminopropane)chromium(lll) pentocyanonickelate(IJ), [Cr(tn)])[Ni(CN),), contains square pyramidal anions. In contrast,
crystalline lris(ethylenediaminc)chromium(JII) pentacyanonickelate(JI) sesquihydrate, (Cr(enh][Ni(CN),) I.SH20, contains both square pyramidal anions (Fig. 12.7)
and slightly distorted uiaonal bipyramidal anions. The IR and Raman spectra of this
solid exhibit two sets of bands. one of which (the TBP se.t) disappears when the
scsquihydrate is dehydrated. In aqueous solution the structure is apparently also
square pyramidal. It would appear that the SP structure is inherently more stable but
Fig. 12.6 TriconDI

bipynmidal struclure ol the
pentachlorocuprale(ll)
1111ion in 1he compound
(Cr{NH,l.J(Cu(:l,). Note
dill'erence in bond le01ths.
[From Raymond. K . N. ;
Meek. 0 . W. ; lbers, J. A.
lnorf. Chtm. 1968, 7,
wich permission.)
Rg. 12.7 Square pyramidal
struccure of lhc pentacyunonickelme(ll) union in .

[Cr(enJ,Jl-ji(CNlsi I.SH,P.
Note che dill'erence in bond
le"achs. [From
K. N.; Co.-field, P. W. R.;
lbers. J. A. lntH'f. Chtm.
1968, 7. 1362- 1372.
Reproducecl wich
permission.)
Coordination Numher S
481
by such a slight margin that forces arising in the hydrated crystal can stabilize a TBP
structure. The forces favoring each of the limiting structures are not completely
understood, but the following generalizations can be made . On the basis of ligand
repulsions alone, whether they be considered naively as purely electrostatic or as
Pauli repulsions from the bonding pairs, the trigonal bipyramid is favored (see Chapter
6). For this reason almost every live-coordinate compound with a nonmetallic central
element (such as PF,) has the TBP structure (unless there are lone pairs), since effects
arising from incompletely filled d orbttals are not present. Likewise, we should expect
d 0 and d 10 to favor the TBP structure. Comparison of the relative energies of the
orbitals in TBP (D,h) versus SP (C4 ,) geometry (Fig. 12.8) shows that d 1, d 2, dl, and
configurations should also favor TBP versus SP as much or more since the t!'
orbitals of o,h are more stable than thee of C4 In contrast. low spin d" should favor
the SP configuration since the e orbitals of the latter are lower in energy than are the e'
orbitals of a TBP complex.te For d 8 the order of stability again switches back to favor
TBP (e' is lower in energy than a 1) and this continues through d" and d 10 Unfortunately. there are few data available to test these predictions. The low spin d 1 complex
[Co(dpehOl+ (dpe = 1,2-bis(diphenylphosphino)ethane] crystallizes in two forms: a
red solid that contains SP ions and a green form that contains TBP ions (Fig. 12.9).19
Ap_parently, the slight ligand field stabilization energy favoring the SP arrangement
0,..-----C,.------C..
Fig. 12.8 Wave runction and energy changes along a Berry pseodororation coordinale. Note
relalive energies of
(D,.) and a1 and e (C4 ,.) levels. (From Rossi, A . R.; Hoffmann, R.
lnorg . Clrem. 1975, 14, 365-374. Reproduced with permission.)
Note, however, lilA! octahedr.U low spin d" and square planar low spin J' arc favored even more.
"Stalick. J . K.; Corficld, P. W. R.; Meek, 0 . W. lnorg.
1973, 12, 1668- 1675.
.S2
12 Coorclinotion Oeonistrys Structure
Fig. 12.9 The sttuerures rl

Ihe red, square pyramidal
Cl
isomer (D) and the crecn
(o)red
Cl
cri&onal bipyrunidal isomer

(b) of the chlorobisj l ,2
bis(diphenylphosphino)elhune)cobalt{IJ) carion.
Phenyl aroups and orher
subslituenrs hove been
removed for clarity. (From
Sr.lick, J. K. : Cor11eld. P.
W. R.: Meek. D. W. lnorg.
Cltem. 1973, 12, 1668-1675.
Reproduced with
permission.)
balances the inherent superiority of rhe TBP arranaement and allows the isolotion of
both isomen. In solurion, the two fonns interconvert readily, either by a Berry
pseudorotation or through dissociation and recombination (see Chapter 6).
Fioally, polydentate ligands can affect the geometry of a complex merely as a
result of their own steric requirements. For example, we find some tetradentate
ligands such as tris(2-dimethylamiooethyl)amlne, (Me6tren c ((CH:J2NCH2CH 2),N),
form only five-coordinate complexes (Fij;. 12. 10), apparently because the polydenuue
ligand cannot span a four-coordinate tetrnhedral o r square planar complex and cannot
conform {.. fold ..) to fit a portion or an octahedral coordination sphere.
Fig. 12.10 Moleculllr

strucwre of bromotris(2
climethylaminoclhyl)amincc.oba.lc(ll) c:ation In
(Co811Me.,lren)]8r. (From
Oi
M.; and Orioli,
P. L. lnorg.
1967,6,
9SS. Reproduced with
permission.]
Coordination Numi>er 5
Site Preference in
Trigonal
Bipyramidal
Complexes
483
We have seen that with nonmetallic central atoms such as phosphorus (tfl}, more
electronegative elements prefer the axial positions or a TBP structure. A molecular
orbital analysis of metal complexeslO indicates that most d" configurations follow this
same pattern. A notable exception is d'. which favors electropositive substituents at
apical sites and electronegative substituents at equatorial sites. In the same way, the
normally weak bonding of axial substituents is reversed with the tf8 configuration.
Thus we find the methyl group in the axial position in the d11 iridiumO) complex shown
in Fig. 12. 11a in contrast to its universal equatorial position in phosphoranes. Also, in
contrast to the phosphoranes, the axial bonds are shorter in Fe(CO)s than are the
equatorial bonds (Fig. 12.11b); however, it must be stressed that there are exceptions
to this behavior (Table 12.2). The same type of analysis2 predicts that in J8 complexes good .....accepting ligands will prefer the equatorial position. The compounds
shown in Figs. 12.11 and 12. 12allow us to test this. Note that most of the ligands occur
in both axial and equatorial positions depending upon what other ligands are present.
Rg. 12.11 Complexes showing apparent exceptions to the rules for trisonal bipyramidal
bondins. (a) The methyllipnd seeks the axial position and ullows lhe strong ,.,. occq,tors to
occupy equatorial positions. Substituent croups on the phoSphine li&ands omitted for clarity.
(From Rossi. A . R. ; Hotrmann. R. lnorg. Chem. 1975, 14. 365-374. Rep-oduced with
permission.) (bl The equatorial bonds in Fe(CO), are slightly looser than the axial bonds.
0
Ill
('
11811"'1
'-....._"<t8J""' t=o
'/ I
? (
,.,
c
m
0
Tobie 12.2
M- l(pm)
Bonci!Hgths in some ell TBP
complens
Complex
Axial
Equatorial
181
18-4
183
188
254
254
182
180
Rossi. A . R .; Hollinunn, R . /norg.

Cltem. 1975, /4, 36S-l74.
"'Rossi. A. R .: Hoffmann. R. /nnrg. Otnn. 1975. 14. 36S-J74.

:a There is in.ufticienl space here to go throush the complete derivation. but it moy be nolcd tilot the
method is not unlike that given l)mliously for octahedral complexes (Chapler I I). For the complete
method, see Footnote 20.
484
12 Coordination
a.....istry: Strvdure
Fig. 12.12 A series or
rriaonaJ bipyr:unidal
complexes which allow a

.,..acceptor eries to be
arranged by notin&
equatorial vs. axial sire
preference. (From Rossi,
A. R. ; Hotrmann, R. l norg.
1975, U, 36S-J74.
Reproduced with
permission. )
l'fhtM<
If we assume that the best .,.. acceptors will always choose an equatorial position, we
can arrange them in the followi"8 order :n

NO+> CO> CN- > SnO)> a-> PRl >
> CH)
This series may be compared with that given in Chapte.r II derived from comple.t ely
dilferent assumptions. The ac:neral concurrence is reassuring.
Site
in
Square Pyramidal
Complexes
In SP geometry the central atom may be in the plane of the basal lipnds or above it to
varying degrees. 'The following discussion assumes that the metlll atom is lying
somewhat above the basal plane, as is commonly found. Under these conditions the
"normal" situation (cf'-4', and
is for the apical bond to be the Slr0"8est with
weaker basal bonds. As in the TBP case, the d' configuration is reversed with strorlger
basal bonds and a weak apical bond . Likewise, good donors usually (tfl_,J6,
seek
the apical position. but in d' complexes electronega tive ligands should prefer the
apical position. The bond lengths shown in Table 12.3 generally support these conclusions although, as before, there are some puzzling exception.s .
If the live-coordinate complex is a result of the addition of a fifth, weakly bound
ligand to a strongly 1r bonded, square planar complex:
(Pd(diarsJ2 !2 +
x- -
Tobl 12.3
lo..d leftgtM in , _ SP
[Pd(diars12Xt
(12.3)
M - l (pm)
c-plo
[MnCI,f[Ni(CN),f-
[lna,r-
Sb(C.H,Js
Apical
losol
d-
198
258
217
242
212
204
d'
230
eft
186
246
222
dl
diO
JIO
Rcssl, A. R.; Hollinann, R. lrtOI'I Ch-.

19'15, /4, .!6$-314..
22 Sine:<: CN- and SnC1] do not

them is Wt<:ertain.
OCC&W
in rile
in this series, rhe incquali(y shown ror
Coordinatioft Numher S
485
then the w-bonding requirements or the former ligands [diars = o-phenylenebis(dimethylarsine)) require that they remain coplanar or nearly so with the metal atom;
hence the SP arrangement is strongly favored.
Five-coordinate complexes with d',
d1 , and d" may be either high a- low spin. The
magnetic susceptibility of the low spin complexes is that expected if one of the d
orbitals is unavailable for occupancy by the metal d electrons. Thus S equals 0 (d8),
l (d'}, 1 (cf>), and i
The magnetic susceptibilities of the low spin five-coocdinate
complexes thus differ significantly from corresponding low spin octahedral complexes. The unavailability of the fifth d orbital can be rationalized in terms
dsp 3
hybrid bonding. The TBP structure results from
hybridization and SP from
d.(l_.pp3 hybridizalion .2l In this sense valence bond theory is in qualitative agreement
with. simple crystal field theory or more elaborate molecular orbital schemes. The
latter two methods, however, also account for the energy levels the other d orbitals
as weU as assign the difference between high and low spin complexes to the relative
energies of the d,? and d_.;-i' orbitals (see Fig. 12.8). The placement of these energy
levels can be reasonably interpreted by means of spectral measurements. In sa-ne low
spin complexes the interelectron repulsions can be neglected to a first approximation
and the spectrum interpreted solely on the basis of the simple one-electron energy
level diagrams (Ftg. 12.13). In the more general case, however, these electron-electron effects must be treated in a manner analogous to that given in Chapter I I
for octahedral complexes.
Magnetic and
Spectroscopic
Properties
or
or
1Aj
..
' '"
. i
---
..,
"''
Fig. 12.13 Spectra or {a) bromotris(methylmercapt<><>-phenyl)phosphinenickel(ll) and (b) bromotris(dimethylarsino-ophenyl)arsinenickei(II) cations. (From Furlani, C. Coord. Chem. Rt'v. 1968, J, t41. Reproduced with permission.)
It is pouible to substitute more J charaCter for p

character and arrive at the same symmetry. For example. d)sp also rums TBP, and d4 s and d'p
also form SP. The aCiual percentages of s, p, and d chanlc:ter will depend 1JP0n energetic factors
such as promotion
and quali!y of overlap of the resulting hybrids.
2l These= the simpkst hybridiz:>liOO$tO visualize.
486
12 Coordinotion a..,.;.try: Structure
Isomerism in
Five-Coordina t e
Complexes
Although it has long been known that various seomeuic and optical isomers are
possible for coordination number 5, examples have been few. We have already seen
examples ofTBP-SP isomerism in an Ni(m complex (page 480) and a Co(ll) complex
(page 481). Another example is
It forms two isome.r s, one orange and one violet, which coexist in solution. Recrystallization from
most solvents (e.g., acetonitrile) yields only the oranse isomer . but dichloromethanel
hexane as solvent yields a mixture of oranse crystals and violet crystals. Both isomers
are square pyramidal, but the orange isomer has the carbon monoxide lisand in the
apical position, and the violet isomer has a basal carbon monoxide wi th one of the
phosphine lisaods at the apex of the pyramid (Fag. 12. 14).lA A related type of geometric isomerism is found in the orsanometallic complex dibromodicarbonytcy
tlopentadienylrhenium(III). Both isomers have the cyclopentadienyl ring at the apex
of a square pyramid with the basal ligands in either a cis or a trans arrangemeot.;IJ
Finally, optical isomerism is even more rare. The first example of the determination of
the absolute configuration of such a chiral complex is shown in F.g. 12. 1S.26 This
Fig. 12.14 Stereoviews of

the inner coontinatioo
spheres about !he central
ruthenium atom in !he
onnac ttop) and violet
Cbonom)
of
CCO). ! From Dcmal. t. ;

Clearfield. A.: Ricci, J . S.
Jr. J. Cryst. Mul. Stn.ct.
t974. 4. 43-54. Reproduced
with permission. ]
1A
1>
z.
llemll. 1.: <lcarfdcl, A.; Rii. J. S ., Jr. J.

Mol. StniCt. 1914, 4. 4J-S4. Clearfield. A.;
Epmin, E. F.: Bernal, I. J. Cl)()ld. Chmt. sm . 6, 227-240 .
Kir1c. R. B.: Reimann. R. H. l1t1Hg. Ch, m.
1976. U, 179-181.
S. J.: Bernal, 1.; a,._, H.; Hemnam. W. A. ilft.f"" Chnn. lftt. Ed. Elotti. 1975. /4 ,
JSJ-1S4. Bernal, 1.; 1..aP1au. S. J.: Karp, J.; Brunner, H.: Hcmnann. W. A.lf!Ofl. Clwm. 1978,/7,
182-18&. Sec also Brunner-. H. ildv.
Ch, m. 1980. 18. ISI-206.
o,,,,..,, ,
Coordinotian Numw S
(aJ
487
(b)
Fig. 12.15 A Schill' base coonplex or dicarbonylcyciOpcnllldienylmolybdenum(ll ) calion.

[From Bernal, 1. ; LaPlaca. S. J.; Ko.,. J.: Brunner. H.: Herrmann. W. A. l 11org.
lll18. 17, 382-388. Reprockld wil.h permission.)
isomer forms along with a dias1ereomer in the reaction of tricarbonyl(cyciOpenta
dienyl)chloromolybdenum with an asymmetric Schiff base:
,,' t''
II
II
'
MoL_',
,,
I.
OC - - - -
Cl
(lz.4)
pfl"
Note that these compounds are not enantiomers, but true diast.ereomers with different
properties, and they may be separated by frac.tional crystallization. The asymmetric
carbon atom has an S configuration in both di:astereomers. but the chirality about the
molybdenum atom is different. Thus the asymmetric carbon aids in the resolution rL
the molybdenum center, but its presence is not necessary for the complex to be chiral.
It is merely necessary for the Schiff base to be
i.e., have one pyridine
nitrogen and one imino nitrogen. If the bid entate ligand had been ethylenediamine.
bipyridine, or the oltllate ion, there would have been a mirror plane and no chirality at
the molybdonum.
488
12Co...dlnation Ch-istry: Strudure
Another interesting elUllllple that combines both geometric isomerism and chirality consists of complexes of the type:n
cts(c:ltiral)
tram (nchirnl)
Note that the cis isomer lacks an improper axis of rotation and is therefore chiral. but
that the trans isomer has a plane of symmetry and will be achiral in the absence of an
asymmetric carbon in the phosplline ligand.28 As in the case of the previously encOOIItered cyclopentadienyl complex (page 476), it can be argued whether the coordination
number is .S or 9. In either semantic interpretation these compounds are of considerable interest since isomerism in nine-coordinate complexes is even less well documented than in those with coordination number S.
Coordination
Number629
This is by far the most common coordination number. With certain ions six-coordinate
complexes are predominant. For example, chromium(lll) and cobalt(IIJ) are almost
exclusively octahedral in their complexes.30 It was this large series of octahedral
Cr(III) and Co(lll) complexes which led Werner to formulate his theories of coordination chemistry and which, with square planar platinum(ll) complexes. formed the
basis for almost all of the classic work on complex compounds. Before discussing the
various isomeric possibilities for octahedral complexes, it is convenient to dispose of
the few nonoctahedral geometries.
Distortions from
Perfect Octahedral
Symmetry
Two forms of distortion of octahedral complexes are of some importance. The first is
tetragonal distortion. either elongation or compression along one of the fourfold
rotational axes of the octahedron (Fig. 12.16a). This type of distortion has been
discussed previously in connection with the Jahn-Teller effect. Another possibility is
elong.ation or compression along one of the four threefold rotational axes of the
octahedron that pass through the centers of the faces (Fig. 12. 16b), resulting in a
trigonal antiprism. Another configuration that is not re.ally a distortion but involves a
reduction of symmetry may be mentioned here. It consists of the replacement of six
unidentate ligands in a complex such as [Co{NH3)J3+ with chelate rings such as
Reisner, G. M.; Bernal, 1.; Brunner, H .; Musclliol. M.; Siebrecht. B . Clwm. Commun. 1978,
69t-692.
2t In fact, chiral
arc ollcn wed in synthesizing moleCtJics dlhis type, both for obscrvina sa eric
effects and for aid in solvina the X-ray crystal suuc:turcs. Sec the dbcussion ol nbsolutc conflsura
ti<>n or lhc previous complex wilh C.N. S nnd octahedral eomplel<CS with C.N. 6 (page 49S).
77
,. Kcpcn, D. L. Pror. lnDrll. Chnn. tm. 21. t-65. Ke.pc.n. D. L. In Comp,.fwniv CoordiMtion
CNmistry; Wilkinson, G.; GDard, R. D.; McCicvcrty, J . A., Eds.; Perpmon: Oxford. 1987; Vol. I,
pp 49-68.
tetrahedral in pmets. occasiooally square planar (page m), or fivc-cOQrdinalc (TBP or

SP). Likewise, Cr(llt) is rarely lriaonal. ICtrahcdral. or TBP.
JO Co{! II) is
Coordi11oti- Numb., 6
'
489
' - o-- - o--- .

'
'
z-in
:-oul
'
o.. - - - - o. - - - - o,.
Fig. 12.16 (a)

and (b) triaonal disJortio ot 311 oculledral ConJplcx. Eilher .-y
occur via elonption or comprusion.
ethylenediamine to form [Co(en),f+. The latter complex has no mirror plane and the
symmetry of the complex has been reduced from 0" to D 3 For most purposes this
reduction in symmetry has little effect (the visible spectrum of the ethylenediamine
complex is very similar to that of the hexaammine complex) except to make it possible
to resolve optically active isomers (see page 492).
Trigonol Prism
Although by far the greatest numbet- of six-coordinate complexes may be derived from
the octahedron, a few interesting complexes have the geometry of the trigonal prism.
For many years the only examples of trigonal prismatic coordination were in crystal
lattices such as the sulfides of heavy metals (MoS2 nnd
for example).ll The first
example d this geometry in a discrete molecular complex was tris(cis-1 ,2-diphenylethene-1,2-dithiolato)rhenium, Re[S 2C1 (C6 H3hh (Fig. 12. 17).31 Following that.
was
a significant series of trigonal prisma1ic complexes of ligands of the type
fully characterized with rhenium, molybdenum. tungsten, vanadium, urconium. and
niobium, and suggested for other metals.))
There is considerable ambiguity concerning the charge on this type of ligand. This
is because it may be formulated either as a neutral dithioketone or the dianion of an
unsaturated dithiol. The difference of two electrons cnn be represented formally as:
.,yS
,...c- c, -
.,..
s,...,_.../s- 1w
...
--R
HS,
<SH
,...e=
(12.5)
Since t.h e electrons involved are delocali.zed over molecular orbitals not only of the
ligand but of the metal as well , it is impossible to assign a formal charge to the ligand or
the metal. Nevertheless, the actual distribution of electron density may be quite
important in determining I!Qw a reaction proceeds, ns suggested for molybdenum
enzymes (see also Chapter 19).3-f
JJ
Wells. A. F.
Slh cd.: Oxfonl Univtnily: London. 19114; p 7S7.

1966. s .fll-4t6.
n EisenberJ, R.; !ben. J. A./. Am. Cltnn. Soc. 1965.87. J776-m8: / IIOIJ.
Soc. 1m. 9S. 7504-7.501.

,.. Bamarcl. K: R.: Wedel. A. C.; Todc.ink. E. R. T . IIIDrf. Clotm. t990. 29. 891-892.
,, Bemeu. M. J.; Cowie, M.; Matlin, J. L.; TablJ. J. J. Am.
490
12 Coordi1M1tion Ch...,i$try: Structure
In addition to the neutral complexes, it is possible to add one, two, or three

electrons to fonn reduced species of the type
Present evidence is that
the reduced species tend to retain the trigonal prismatic coordination with some
distortion towards a regular octahedron with increasing addition of electrons (see
Table 12.4).
One of the most interesting features of the I ,2-ethenedithiolate or 1,2-dithiolene
complexes is the short distance between the two sulfur atoms within a chelate ring.
This distance is remarkably constant at about lOS pm, some 60 pm less than the sum of
the van der Waals radii (Table 8.1), indicating the strong possibility of some S-S
bonding that may stabilize the trigonal structure.JS One way in which this might come
about is by pulling the sulfur atoms towards each other, reducing the bite angle (it is
about 81 in the complex in Fig. 12. 17).
octahedral coordination requires 90".
Another way to look at it is to imagine the molecule in Fig. 12. 17 undergoing a 6IJ'
twist of one of the S 1 triangles to form an octahedron. lf the other dimensions remain
the same, the sulfur atoms would have to move aWaY from each other, and this would
be inhibited if there is any
bonding.
There are few trigonal prismatic complexes with unidentate ligands. but both
[Zr(CH 1)J2 - and W(CH1) 6 have D symmetry. as shown in the margin.l6 The factors
favoring olt symmetry and inhibiting trigonal distortion are not difficult to see: steric
effects of bulky ligands. large partial charges on the six ligands, and relatively small
metal size. To be sure, these are absent in these hexamethyl compounds and in the
hypothetical CrH., studied by ab init.i o calculations. The factors favoring Dl/0 symmetry are more subtle: for example. the relative stabili:zation of
nonbonding
orbitals similar to that in the MO analysis of BeH 2 and H 20 in Chllpter S .l'
c,
s-s
Tobie 12.4
Mop of twist angles (II) in lltt(dnhiolato)metol .....,..x.., Mt:;-
Group lVI (41
IZrq-
Group VB (51
Group VII (61
G.oup VIII (7)
Group VIlli (81
0")
(9 , 19.6") NbL) (8 = 0.6)
MoL,(9 ()")
TaL; (8-J6")
(8- 17.0")
0")
TeL, (9 4.6)
Mo!J- (8 14.0")
(8 .. 14.0"1
(8- 24.5")
Tfilonal prism, II 0': octabedcon. e 60"
" For reviews of COI11plucs conW..U. 1hcae lipnds, see rcl'erences in Footnote 29.
""Morse. P. M.: Girolami. G . S. J. Am. Clrtm. $. 1918. Ill.
Haaland, A.; Hammel. A.;
Rypdal. K. ; VOlden, H. V. J . Am. Clltm. Soc. 1990, 111. 4'-47-4549.
n Kana, S. K.; Albri&hJ. T . A.: Eisenstein. 0 . lnort. Clwm. 1919. 28. 161 H61J.
Fig. 12.17 Slt\ICtUre of
[Rc(S.C,PflthJ, The phenyl

rinp have been omilted for
clarity. (From Eisenberx.
R. ; lben, J. A. fng.
Cl,m, 1966. J. 411-446.
Reproduced with
permission.)
Geometric
Isomerism in
Octohedrol
Complexes=-
Tberc arc two simple types !:X geometric isomerism possible for octahedral complexes.
The first exists for complexes of the type MA1 B4 in which t.h e A ligllllds may be either
next to each other (Fig. 12. 18al or on opposite apexes of the octohedron
12. 18b).
Complexes c:J this type were studied by Werner, who showed that the praseo and
11ioleo complexes of tctraamminedichlorocobalt(lll) were of this type (sec Chapter II).
A very large number of these complexes is known, and classically they provided a
fertile area for the study of structural effects. More recently there has been renewed
interest in them as indicators of the elf'ects of lowered symmetry on electronic
transition spectra.
Two geometric isomers are also possible for complexes of the type MA 1 B1: (I)
Tbe ligands c:J one type may form an equilateral triangle on one orthe faces (thefadlll
.::: ::::
NH1
cis
C'l
.......
I I
lbl
Fig. 12.18 Examples or cis and trans octahcclr:tl isomcn: cal cis
tetrunvnincdichtorocoball(l ll). Werner's vio/, o complex, and (b) "ans
lelraammincdichlorocobah(IIIJ. Werner's
complex.
" For a full discusaion d acome1ne isomerism, sec Saito. Y. ffiOfJ'Jflk ltlol,cular Dissymmnry.
SptqerVeda,: B<rlitl, 1979; pp6-7, 73-a.
492
12 Coonlinotion Cheistry: Strveture
:::
H,O
facial
H,o
mcridionat
(I)
Fig. 12.19 EllaJllples of facial and meridionlll oclahedr.ll isomers: (a) /actriaqu:urichlororuthc.n ium(llt) and (b) mtrlriRqualrichlororulhcnium(lll).
isomer, Fig. 12. 1911, abbreviaJcdfoc in the nnme) or (2) they may span lhree positions
such thnttwoare opposite. or trans. to each other (the mtridionol isomer. Fig. 12. 19b.
abbreviated mtr in the nnme).39 In contrast to cis--trans isomers of MA,B., which
number in the hundreds, far fewer facial-meridional isomers have been chmcterized;
examples are [Ru(H 20)3CI1). [Pc(NH 3) 3Br3]+, [Pt(NH,),I,t, [lr(H20),0J,
[Rh(CH3CN),CI3), [Co(NH,)iN01 ),) , ond (M(CO),(PR3),) (M = Cr, Mo. W).
Optical Isomerism
in Odahedral
Complexes
It was mentioned above that tris(chelale) complexe.s of the type (Co(en),f+ lack an
improper axis of rotation. As a result, such complexes can exist in either of lwo
enantiomeric forms (or a racemic mixture of the two). Figure 12.20 illustrates the
complex ions (Co(en),J1 + and (Cr(ox)3] 3- , eoch of which is chirnl with D1 symmetry.
It is not necessary to have three chelate rinls present. The cation dichlorobis(ethylenedinmine)oobalt(lll) exists as two geometric isomers, cis and trans. The
trans isomer has approximate Dv. symmetry (Fig. 12.21b). Because it has three
internal mirror planes, it is achiraJ .oo 1lle cis isomer has C1 symmetry and is chiral
(F"tg. 12.21a). Since the two chloride ions replace two nitrogen atom.s from an eth0
..t .f
o.::::r,.Oo
?0
Cr
o" 'o
o,c,...c..,.o
u
0
Fig. 12.20 Structures oC the oplically active eomplcxe.a (Co(cn),],. and [Cr(ox))J'- (one
enantiomer oC each) and a styliud drawiog of lhe two
of any Iris( chelate)
complex.
arc also sometimes calcd cl$-lrans isomcn. but the fee> mer nomencta1urc is
However, lhc IUPAC recomrnendaliclns arc moYi111 away from the use oC 1cnns like facial and
J9 These
meridional
USUIIIC$....,.
.., This
the cthylcne<liamine-mc .W.S arc Slrietly pltA&r. which they arc 1101. We shoD
sec lhal these riolts arc skewed. However. since the two
forma irt..-wcrt rapidly, for
po.w]I05CS oC OJl(icaJ actmly, the C00'4'0Und bdlaves IS lhouah it wen: acbinl.
cw
Coonlinotion Number 6
f!\!c
493
Co
Ct
MinO<plon<
tal
MirTO< piAn<
(bt
Fig. 12.21 (a) Optical isomers of t"is-dichtorobis(ethylenediamine)coball(llll ion

sait1.
(b) trolts-Dichlorobislethylencdiamine)Cobalt(llll ion (prouo snh) showing one internal plane
of symmetry (Chere are two others perpendiwlnr to the one shown).
ylenediamine ring with<ltlt disturbing the remaining geometry, the optical activity is
preserved. For purposes of dissymmetry, the change of two nitrogen atoms to
two chlorides is insignificant. Further replacement of chelate rings by paired unidentate ligands can take place as in cis-cis-cis-[Co(NH,)z(H20MCN>2 which is chirai;<Z
but in ordinal)' practice the resolution of enantiomers is limited to complexes containing chelate rings. The chelate rings provide the complex with additional stability
(see ..The Chelate Effect,'' page .522). In addition, the nonchelate complexes are diffi
cult to synthesize, and it is also difficult to separate the large number of geometric
isomers.
Werner synthesized and resolved optical isomers as strong corroborative evidence for his theol)' of
coordination. Although he did not discuss the
subject in his first paper. the idea appears to have come to him about four or five years
later. ) and he was able to resolve amminechlorobis(ethylenediamine)cobalt(lll} calion (cf. Fig. 12.21 with one chloro group replaced by ammonia) about fourteen years
after he first became interested in this aspect... Werner realized that the presence of
enantiomers in the cis but not the trans compound was incompatible with alternative
formulations of these complexes. He succeeded in resolving a large Seiies of complexes including Co(lll), Cr(lll), Fe(ll), and Rh(lll) as metal ions, and ethylenediamine. oxalate, and bipyridine as chelating ligands. Nevertheless, a few of his critics
pointed out that all his ligands contained carbon. By associating optical activity
somehow with ..organic" versus .. inorganic" compounds and ignoring all symmetl)'
arguments, they proceeded to discount his results. In order to silence these specious
arguments, Werner synthesized and resolved a polynuclear complex containing no
carbon atoms, tris[tetraammine-p.-dihydroxocobalt(lll))cobalt(lll) (Ftg. 12.22).s This
r,
., The "replllccment" of dhylenedinminc by chloride ions, cited '-e is a

reaction
and refers to the formal change. II does not imply thai in solulion two chloride ions could anao:k a
41
ICo<enl,l' calion with retention d conliauration.

ho. T.; Shibata, M. lnnrg. CJ.-m. tm. /6, 108-116.
Werner mcnticncd the possillility in a leuer to

coworicer Arturo Miolali in 1897. See C/Duics In
CoordinaJioo Chtmbtry; Kauffman, G. B., Ed.; Dover: New Yoric, 1968; pp ISS--158 .
.. Werner, A. Clttm. B.r. 1911, 44. 1887. A translalion may be found in Q,.sics in Coordinal/on
KauiTman. G. B., Ed.; Dover: New York, 1968; pP tS9-173 .
., Werner. A. Chtm. Bn. 1914, 47, 3081. A translalion may be found in Oassics in Coordinotion
CMtrlistry; Kauffman, G . B ., Ed. ; Dover. New York, 1968; pp tn-184.
494
12 CoDI'dl...,liCM! Clutmiotry: Slrvclure
Fig. 12.22 One c....,uiomcr

ollhc trisllelr:lllmminc>,...
clihydroxocobab( 1111)
c:olx>IJ!III) calion.
laid to rest the d istinction between carbOn and the other elements that should have
died in 1828 with W6hler's work. It is interesting to ne that in all of the work since
Werner only one other completely carbon-free complex has been resolved, sodium
cis-diaquabis(sulfamido)rhodate(lll) (Fig. 12.23),46 chiefly because of !he difficully of
preparing noncnrbon chelating agents,
Resolu1ion of
Opiically Active
Complexes
Few inorganic chemists have been as lucky as Pasteur in having their Opticnlly active
compounds crystal lize as recognizable, hemihedral crystals of the two enantiomers
which may be separated by visual inspecJion ..n Various chemical methods have been
devised to effect the resolution of coordinalion compounds. Tiley all involve interaction of the ennntiomeric pair of !he racemic mixture with some other chiral species.
For Optically act.i ve cations. interaction with one enantiomer of n chiral tnrtro1te.
abromocamphor....r-sulfonate, or one ennntiomer of a metal complex anion will result
in differentially soluble diastereomers, the shifling of equilibria in solution , or various
other changes in physical properties that allow the seporation to be effected. For the
resolution of an anion, chiro1l bases such as strychnine or brucine (protonated to form
cations) may be used. Neutral complexes present difficulties since it is generally
impossible to form salts. Differential physical properties toward dissymmetric substrates moy be employed such as preferential extraction into a dissymmetric solvent or
preferential adsorption chromatographicaly upon quartz. sugar (both consisting of a
single enantiomer), or ocher chiral substrate.
0
\\
,.....s
Fig. 12.23 One enan10omer

otthe ri.<diaquubis(sulfamidolrhodlltc(lll)
anion.
liN-.
s.:::::o
II
.. Mann. F. G. J. Chtm. S. 1933, 4t2.

., However, some rdali..,.y si...,te c:obal1 C01J1plucs such os
cobaii(IU) salas Cl<hibil lhis behavior. Some of Jhcsc wert prtpercd by Wtrner and wert. unltaown
10 him, resolvir1a lhcmsctves sponlanCOUSiy as he rutys(olliud Jhcm. This occurTcd at 1he very
1ft Jhat he was spo:.C,. 14 )'Un punui,. the resolulion o(
Sec Bernal.
1.; Kaulfman, G. 8 . J . CIH!m.
1987. 64. 604- 610.
Caordi,.atian Number 6
4 95
The determination of the absolute spatial relationship (the chirality or ''handedness")

of the atoms in a dissymmetric coordination compound is a problem that has intrigued
inorganic chemists from the days of Werner. The latter had none of the physical
methods now available for such determinations. Note that it is not possible to assign
the absolute configuration simply on the basis oflhe direction of rotation of the plane
of polarized light,4H although we shall see that. through analysis of the rotatory
properties of enantiomers, strong clues can be provided as to the configuration.
Before discussing the methods of experimentally determining absolute configurations. let us briefly discuss means of denoting such configurations. As was the case in
organic chemistry, these rules grew up before much was known nbout the absolute
configurations. so they leave much to be desired in terms of logical interrelationships.
The simplest method. already mentioned, is notation of the experimental direction of
rotation of polarized light, ( +) or d, or ( - ) or I. Thus one may speak of ( + >,39which is dextrorotatory with respect to light of wavelength equal to
.589 nm. 49 This label identifies enantiomers with respect to each other. but serves little
purpose otherwise, although we shall see that by using certain techniques and assumptions. strong clues can be provided with regard to configuration.
Next, as in Emil Fischer's system for o-&]yceraldehyde and sugars. we can
arbitrarily assign the o configuration to ( + )-[CO(en);JJ+ and compare all known
conligurations with it. This now invnediately tells us the configuration of a o-isorner
(by comparing it with a figure of
). but the o symbol is an arbitrary one
that could have as readily been zzz versus www. F\Jrthermore, it can even seduce the
unwary into thinking that o has somethinG to do with being dextrorotatory" or
having "tight-handedness."
A systematic basis can be gained by viewing a tris(chelate) complex, the most
common species of chirol coordinruion compounds, down the threefold rotation axis.
If the helix thus viewed is rigJlt-handed. the isomer is the A-isomer. and its mirror
image is the A-isomer.,., The o-, L, A. and A-isomers may thus be portrayed as
o.
6 or L isomer shown in the margin. Note that it is a result of these systems that A "# Land A
furthering possible confusion.
In ordinary X-ray diffraction work both enantiomers give exactly the same diffraction pattern, and thus this method gives no information on the absolute configuration
about the metal atom. However, absolute confisurations of coordination compounds
can be directly de1ermined by means of the anomalous dispersion of X rays, called
Bijvoet unulysis.,l The method hns not been widely applied, but llS in the related
problem in organic chemistry of the o.bsolute confisurution of o-&)yceraldehyde, once
absolute configuration is known, there are methods to correlate others. The absolute configuration of o-( + ){Co(eni,)J+ has been determined as the chloride o.nd bro-
Absollrle
Configuration
of Complexes
1\ Of D
isomer
For example. il is known lhallhc enanoicmcn ol

onciiRhlcnl,f. which rou1e sodium
0 lip! in Ihe same clircclion, hove 1he opposi1e obsotu1e alelfiauraJlon; i.e .. Ihey ore of opposiJe
handedncss-mirTOr imqcs of each 01hcr licnorlna 1he dill'cffii<)C belween Co and Rhl.
.. This is I he "sodium 0 line." For h. 100. 1hc "0" has nolhina 10 do ..;1h "duarorOhlory." Since
1hc sodium D line is so frcqucnlty used, reference 10 il is o/lcn omillcll, bul other wavclcnslhs
should dways be cxplicilly swed.
'"This svgestian..,.. made by Piper, T. S. I . Am. Chtm. Soc. 1961. &J. l9011-l909. The IUPAC
""ICOided 1his td a c:onsidcrollty more acncnliud
Appendix 0 .
FOC" lris!dldalcsJ bolh s}'SianS han lhc same de. .naJion, as ajven abo..,.
" Bijvoet. J. M.
14. 71-77. Sec also Saico, Y. lnortunk /tio/KU/tv Dissyii'IIMtry;
Springer-Vedq: Jlertin, 1919; Chapler 2.
498
12 Coordination O.emistry: Slnletu,..
(0)
IJ
I,
',' :I
\
(b)
_,"
+
,I
,,
,,
\I
\ ,
lt!O 1----------.--'--...,..-----IAo
Fig. 12.25 The Collon clfect: (a) positive Collon etrect: (b) neptive Cotton efrcet. The
absorption band is 1101 shown: il woWd be a pOsitive GauAian curve centered 011 A-.. but
off scale. 11lc dashed line represents the ORO curve (and relates to the refractive Index seale
on left). The $Oiicl line represents the CD curve (c 1 - c.. sc:lle on rishl). The maximum
absorption. zero values o( ORO. and maxima and minima o( CO values occur a1 A..,... The
1wo fisures . (a) and (b), represent two enan1iomers. These are ideal curves ror an absorption
peak weU sepanted rrom other absorptions. (Modil'ied rrom GillArd, R. D. Pro11. lnorR.
Chrm. 1966.. 7. 215-176. Reproduced with pennission.)
Although ORO was used extensively at one lime because or simpler instrumentation. circular dichroism is currently much more useful . The CD effect arises because
there is diffe"ntial ubsorplion or left and right circularly polarized light associated
with transitions such as 1A 1 -+ 1 and 1A 1 -+ 1A1 The circular dichroism is the
difference between the molar absorptivities or the left and right polarized light.,, - '
(solid curves in Fig. 12.25).56 Compltxts having tht samt sign of CD for a givtn
absorption band will havl! thi! samt absolutl! configura/ion. Some typical values are
listed in Table 12.5 .
Stereoselectivity ond
he Conformotion of
Chelote Rings
In addition to the dissymmetry sene rated by the tris(chelate) struclure of octahedral

complexes, it is possible to have dissymmetry in the ligand as well. For example, the
gauche conformalion of ethylenediamine is dissymetric (rag. 12.27) and could be
resolved were it not for the almost complete absence of an energy barrier preventing
"' Sometimes the value o( -.,is givrn as 64. l r to. is positive (c 1 > c,), il is called a po.!itlve Concn
effect, etc.
Coordinolion Nu.,.her 6
499
)(
0
-1
::!
_,
400
400
,.,...soo,
(&)
667
400
).
,....,
SCJ()
600
(<)
(bl
Fig. 12..26 The absolule c:onligur.uions and ORO spectra ol (a) A (Co<enh)' ; (b) A(Co<S<S...., - the union of S-(U-atminel: (C:l A(Co(en):(S-slulr IS-stu = the dianion ol
S-(L}-&Iutumic acid). AU ol these complexes h3ve the A oro c:onficuralion.
Table 12.5
Circular dichroism dolo

for some A-(o)- ond A(l)
tris(chelote) complexes of
cobolt(UI)o
Absolute
configuroti""
",,.,-,,
E1 -
( + )3K9-(Co(en),Jl+
20,280
23,310
+2. 18
- 0.20
( - ),,..-(Co<en)J),..
20,280
23.310
- 2. 18
+0.20
A"
( + ),K9-(Co(S-pn),J,..
20,280
22,780
+ 1.9S
-O.S8
( + )SI!9-(Co(R-pn>,J' +
21,000
+2.47
( + ),89-(Co(S-ata),J
18.500
2 1,000
+ 1.3
-0.2
/1.
/1.
( + )49,-lCS-81u)(en)1 )2+
19,600
+2.S
Formulo of complex
Saito, Y.
Dluymmtlry: SprillJer-Vetlaa: Bettin,
1979; p 136. N01e Jhat ahe aril(alll) complex has D dilrcrent chrornophore
(CoN,O:,) lllan ahe lris(diaminc) t001)1txes (CoN.J. and so the
resemblance is only approximue.
hen e lllylcncdiamine; pn - propytcncdiaminc: ela alaninate;
aJu puwnale.
Since in eacfl case the isomer wiU have the same Yalue wilh oppo
sign ror ils spu:i/lc totalion, the same value ror ahe
muim>m,
and the-same valuc(a) wilh oppo:sice sisn ror the circuJIIr dichroism
compared to the A isomer, lhese values are not aU listed here.
t
500
12Coonlinallon Q-islry: Structure
Fig. 12.27 Enantiomeric

conformations of
ethylenediamine (1,2diaminoethane). Note thllt 8
represents a right-handed ,
helix and A a left-banded
helix.
racemization. Attachment of the chelate ligand to a metal retains the chirality of the
gauche fonn, but the two enantiomers can still interconvert through a planar conformation at a very low energy, sinular to the interconversions of organic ring systelllSThus, although it is possible in principle to describe two enantiomers of a complex
s\ICh as [Co(NH:J4 (en)Jl .., in practice it pcoves to be impossible to isolate them
because of the rapid interconversion of the ring conformers.57
If two or more rings are pcesent in one complex, they can interact with each other
and certain conformations might be expected to be stabilized as a result of possible
reductions in interatomic repulsions. For example, consider a square planar complex
contain in&. two cbelated rings of ethylenediamine. From a purely statistical point of
view we might expect to find three structures, which may be formulated Mllc5, M.\.\,
and Mil.\ (which is identical to MAll). The first two molecules lack a plane of symmetry, but Mil.\ is a meso form. Corey and Bailar'e were the first to show that the MIJIJ
and MAA should predominate over the meso form since the latter has unfavorable
H- H interactions of the axial-axial and equatorial-equatorial type between the two
rings (Fig. 12.28). The enantiomeric M/J/Jand M.U forms are expected to be about 4 kJ
mol-1 more stable than the meso isomer, other factors being equal.
More important consequences result for octahedral tris(chelate) complexes.
Again, from purely statistical arguments, we might expect to find M881l, M/J/J.\, MIJ.U.
and MA.U forms. In addition, these will all be optically active from the tris(chelate)
structure as well. so there arc expected to be eight distinct isomers formed. In general,
a much smaller number is found, usually only two. This stereoselectivity is most easily
followed by using a chiral lignnd such as propylenediamine, CH,CH(NH2 )CH2 NH2
The five-membered chelate ring will give rise to two types of substituent positions,
those that are essentially axial and those that are essentially equatorial. All substituents larger than hydrogen will cause the ring to adopt a conformation in which the
substituent is in an equatorial position. As a result of this strong confonnational
propensity, R-(- )-propylenediamine boods preferentially as a .\ chelate and
S-( + )propylenediamine bonds as a ll chelate. This reduces the number of expected
isomers to four: A-M8IJIJ ( = o-M8IJIJ), A-M.\.\.\ ( - o-M.\.\.\), A-M8IJIJ ( L-M881J), and
" Note lhal in this case lhe chirality is not clue 10 the atraJliCmcnt about the m1tal a10m, but resulll
from the 6
A chinlGiy ol the elhylcncdiamine-mo:181 rins. See Shimura. Y. Bull. Chrm. Soc.
(Japan) 1958. Jl. 311 .
""Corey. E. J.; Bailar. J. C . Jr. J. Am. Chm. Soc. 1959,81.2620-2629. This is lhe classic paper in
the field upon w!Wch nit or the subsequent worlt has been based. See also Saito, Y. Inorganic
Moluulnr
Berlin. 1979; Chapter 3.
C-dination Numb. 6
tal
501
(bl
Fig. 12.28 Conronnotional interaclions in bis(chetate) square planar complexes: (a) J.J. ronn:
atoms ucepl four have been omiUed ror grcater clarity. Dashed
(b) Ali form. All
lines n:presenl intcr.flng H-H repulsions. (Modified from Corey. E. J.; Bailar. J. C. , Jr.
J. A.m. Chern. Soc. 1959, 81, 2620-2629. Reproduced with permission.]
A-MAAA ( = L-MAJ.J.) where A, A, o, and L refer to lhe absolute configuration about

the metal related to A.{ + ).m-fCo(en),f+ ( .. !he o en&nOOmer; see Fig. 12.26). In a
typical reaction such as the oxidation of cobalt(m chloride in the presence of racemic
R,S-propylenodiamine. only two isomers were isolated:
[Co(H20)&f+ + R-pn + S-pn
A{CoCR-pn),f+
(12.7)
The difference in stability between the various isomers has been related to
preferred packing arrangements of chelate rings about the central metal atom. Thus,
for S-propylenediamine forming a 6 chelate ring, the most efficient method of fitting
around a metal will be in the form of a left-handed helix. This arrangement minimizes
!he various repulsions. 1t has been termed !he ltd isomer since the
bonds are
parallt!lto !he threefold axis of the complex (Fig. 12.29). The alternative isomer. in
which the ligands form a right-handed helix about the metal, is known as the ob isomer
since the C-C bonds are oblique to the threefold axis (Fig. 12.30).'9 The interactions
c-c
Fig. 12.29 The lei

conformer or the A or o
enanliomer or trill(diaminc)
metal eomplues. The
hatched circles represent
the positions or the mdhyl
groups in the propytenediamine complex. For
propytenediamine, this
represents the 11688 or o688
isomer. (Modified from
Corey, E. J.; Bailat. J. C.,
Jr. J . Am- Chem. Soc.
t95!1. 81, 2620-2629.
Reproduced with
penniSJion.I
"Specifically .-.ce there are three chelate: rinp, each d which can ,ottntUUiy be eilba-111 or ob,
rwo iso""'" sllould M labeled 8$ ltl, and ob, liJic:e it i6 possi>te to ha\'C mixed ol>-ltf
eomplex.es.
502
12 CoordiRatiOR Chemistry: Structure
Fig. 12.30 The nb

conformer
or 1he 11 or L
illomer or lris(diamine)metul
complexes. The hatched
circles represent the
posillons the methyl
&rOUp$ in I he propylcnediarniRe complu . For
propylenediamine this
represents 1he b&/i or L&/i
or
isomer. (Modified from

Coc-cy. E. J.; 8uilar. J . C..
Jr. J. Am. Ch,m. Sex:.
1959. 8/, 262()..2629.
Reproduced with
penniuion.)
or
nnas
bcJween the hydrogen atoms

t.h e various
stabiliz.e the /e/ isomer by a few
kilojoules per mole. NOie that this greater stability of the one conligur.11ion over
another is the source of the stereospecific s ynthe.s is of A-tris(R-propylenediomine)cobalt(II O seen previously (paae 496).
Asym metr ic
Syntheses Coto lyzed

by Coordina tion
Compounds
or
There has been considerable interest in the stereospecific synthesis

Ofl'lllic compounds using optically active coordination compounds. Chiral catalysts are sought for
the production 0( drugs, pesticides, pheromones. and fraranccs . Quite recently a
signitic:lllt advance was made with the discovery that asymmetric epoxidaJion can be
achieved with maoganese(lll ) complexes containing chiral chel:ting agents. One of
the catalysts used is generated from manganese( ll ) acetate, CR. R')- or (S. S' )-1 .2diamino-1.2-diphenylethane, a substituted salicylaldehyde. and lithium c hloride. In
the presence of this catalyst and sodium hypoch lorite. a lkenes are converted to
epoxilks:
(12.8)
R 1
R!. W = H. alkyl,
aryl
R = Ph
X H, OMe. Me, Cl. N02
90"-'
Some cis substituted al kenes can be convertetl to chiml epoxides in greater than
enantiomeric excess by this process.HI
E. N .: Zh-. E. : GOicr, M. L. J. Am. Chtm. SM. tt91, 111.610}-6704. Fcr:Jddilion:ll

BoMlich. 8 .: Fryzuk. M. D.
Top. Stntoclrtm. 1911, 12.
K.apn. H. 8 . In Comt"thtnslor Or!/atu>m<'tll/lk Chtmistr;r:
Wilkinson. C.: Slone. F. C. A.: Ab<l. E. W.. Eds.;
Oxford, 1982: Vol. B.. pp 46}..498:
Scou. J. W. Top. Stwtod.,m. 1989, 19. 209-226,
00 Jacd>scn.
..
- - -----
Cocwdination Number 7
Col
(d)
(bl
(cf
(el
( I)
503
Fig. 12.31 The chiral diphtphine ligands (a) R .R ( -1-diop. tbl R-l ... 1-binap. and
(c:)
S-<- H>inap. The free tisands are shown at the lop and coordinated to a modiumcll
or ruthenium( Ill a1om. below:
(d) CR.R-{ -kliopJRh(IJ moiety. Cel ($-(moiely. Note the chirality foced by incoming liCllnds. The vi<!w is down Jhe C: axis.
(I) (S-i - )-binaplbislcnrboxybto)l'tllhcnium(ll) looking down the pS<!udo-D,
Hydrogenation of double bonds using a rhodium(!) catalyst (see Chapter 151 may
be carried oot stereospecifically using a chiml diphosphine such as "diop" or ..binap"
(Fig. t2.31 ). The chirality of the diphosphine makes the two possible ransilion states
(leading to the two enantiomeric products)
and therefore subj<!cl to
differences in equilibrium concentrations, energies of activations. and react.ion ratesone cnantiomeric product may thus form to the exclusion o f the other. The
(diop)Rh(l)-catalyzed enamioselective hydrogenation is used commercially to make
S-(LJ-OOPA. a drug used 10 treat l'llrkinson's disease. and
[S-h.lphenylalanyl-.HI.I-aspartic acidl. an artificial sweetener. The Jbin:tpiRullll c:ualysis may
become even mnre useful."'
Coordination
Number
762
Coordinlltion number 7 cannot be considered a t all common . The relative instability of

these species can be attributed to the fact that the additional energy of the seventh
bond is offset by (I) increased ligand-ligand repulsion. (2) weaker bonds. and (3)
generally reduced ligand field stabilization energy as a result of nonoctahedral geometry. T here are three geometries known: ( I ) a pentllgonal bipyr-.unid !Fig. 12.321. which
is also found in the main-group compound IF7 (Fig. 6 . 12): !2) a capped octahedron in
which a seventh ligand has been added to a triangular face (Fig. 12.33): and (3) a
Noyori. R. Sclrnc<' 1990. 248. 1194- tl99. NoyOti, R.; Tokaya, H . Ace. Cltrm. Rtt. l9'XI. 21,
J.4S-3SO. Brunner, H. Tnp. Strtm:lrtm. 1988, 18, 129-247.
6Z
Kepen, 0 . L. In Comprtltrnsiv<' Coordination Chrmistry: Wilkinson. G.;

Cievuty, J. A . Elk.; Pergamon; Oxford. 1987: Vol. t, pp 69-83.
R. D.: Mc-
504
12 CoordiRoliaR Qemistry: Structure
Fig. 12..32 Molecular

sJrUclurc or the seve,, ..
coordinate complex ol iron
involvina 2. 11
dimcthyiJ,6.9,12,18pcnJaazabicyclol( 12.J. I)
octndeca l( 18),2, 12,14.16pcntaene and 1wo axial
SCN - Jiaands. Hydrogen
atoms omiucd. (From
Fleischer, E.; Hawkinson,
S . J. Am. CMm. Soc. 1967,
89, 720-12 1. Reproduced
wilh permiuion.)
Fig. 12.33 The molecular

unil ol lril(diphenylpropanediooaiO)aquabolmium(lll) projled down
1he
axis. The
waler mold:ulc is direaly
above the holmium atom
but hll$ been displaced
alighUy in this dnlwina to
sllow Jhc slructurc better.
(From Zalkin. A.;
Tcmplclon. D. H.;
Kamker. D. G . lnorg.
Chtm. 1969. 8. 2680-2684.
Reproduced wilh
permission.!
capped trigonal prism in which n seventh ligand has been added ton rectangular face
(F'Jg. 12.34). They are of comparable stability nnd easily interconvef'lible. Therefore
there are also many intermedillle cases, and the situation is reminiscent of livecoordinate geometries.
In many ofthese complexes the requirements ofpolydentate lignnds fnvor coordination number 7. Thus it is not difficult to see the effects of live mncrocyclic and
copllll'lllr nitrogen atoms in Fig. 12.32 on the resulling pentagonal bipyramidal structure. In some cases. even unfavorable interactions mny be forced by the ligand
geometry. For ex,ample, in one type of seven-coordinate complex, it appea.rs as
though the seventh coordination, forced by the geometry of the other six coordinating
llloms, might in some cases better be considered as an "nntibond" raJ her than n bond.
This effect is seen in the series of[M(py,tren))1 + complexes (M : Mn, Fe, Co, Ni,
01, Zn; py,tren = [CsH4 NCH-NCH1CH1],N) in which the three imine nitrogen
c-dination Numbllf' 7
5 05
12.34 Structure of the

heptaftuoroniobnlet V)
anion. [From Hoard. J. L.
J. Am.
Soc. 1939.
61, 1252. Reproduced with
pcnnission.)
atoms are at the vertices of one equilateral triangle and the three pyridine nitrogen
atoms are at the vertices of another.6) One could refer to this arrangement as an
approximate octahedron, but since I he metal ion is closer to lhe imine nitrogens than
to the pyridine nittogens, it is best to refer to it as a trigonal antiprism
12.35).64
Even that is not a perfect descripeion
there is some trigonal distortion
(rotation of opposing
faces tending toward a trigonal prism) in each com-
tat
lb
tel
Fig. 12.35 (M(py1 tren))>+ complexes: (a) The py 3tren ligand:
the nitroaen atoms are labeled

N,.. the pyridine nhroacn. N1 the imine nitroaen. and N,, the seventh or unique nitroaen atom: (b) o diagrammatic:
represeniBiion of the (M(py,lrenlf complex, viewed down the threefold nxis: (c) the molecular structure of the zinc(IJ)
complex. viewed perpendlcular 10 the threc:Cold axis. (Counny of E. C. l.ingafcher.)
Ol Kirchner. R. M.: Mealli, C: Bailey, M.; Howe, N.: Torree, L P.; Wilson, L. J .; Andrews. L. C. ;
Rose, N. J.: l..inpfelter. E. C. Coord. Cllrm. R'" Its?, 77, 89-163.
" NOJe thai an ocl:lhedron is a special cue oftriconal onlipri1m in which all edges have lhe same
lenalll. However. in connsc to the usual choice of coordinlles (A-, y, and t lie on the l'oulfold axes
ror an ocl:lhedron). the lqhest fold axis in a trilonal antiprism is, In general. lhe Jhreefold al<ls
which is assianed 10 the taxis. N01c llw (e.xcepl ror lhe choice of coordinates and correspondinc
(Chapter Ill: lbrcc lower
lllbds) 1hc lrigonal $1)1illina closdy resembles a pscudooctahedral
Olbitals, at and lr
in 0) and two hisher orbitals,
(' in O.). The dJa:t of lrigonal
anaiprismalic: ctislortionon the relative energy of the " Of1);W wilh respcc110 the lr
orbital$
will depend upon the
of the de> orbital with the Nr lone poir orbillll. II is shown above as
ahan r,, but illw been suucsted thai in some oCthesc c:ompkxes it may lie b<lwccn 1, and
'U. As in the octahecnl case," bonclina can be added 10 the a-only system.
506
... Ch_O., -
plex. The o--<>nly ligand field splilling pattern for a trigonal antiprism (D3)
three levels, the a 1 (di ), le
and the 2c (dr. d,,.>:
2e (d= d,,>
le
l
j
, d-<Y)
a 1 (dt >
The lone pair of the tertiary amine nitrogen atom (N7) capping the trigonal antiprism is
directed at the center of a trigonal anti prismatic face and thus interacts directly with
the u 1 orbital.
Figure 12.36 illustrates the metal-nitrogen distances in this series of complexes.
The upper trace represents the M-N7 distance. An increase in electrons in
directed at any of the seven nitrogen atoms causes an increase in bond length.'
Specifically, in the case of the Fel+ complex, the only low spin complex in the series:'
there is a dramatic decrease in one distance and concomitant increase in the
The low spin (u 1) 1( 1e)4 configuration maximizes electron density toward lhe axial
nitrogen while minimizing it in the direction of the trigonal antiprismatic nitrogen
atoms.
1
The M-N7 distances for the nickel, copper, and zinc complexes (323. 311, and
301 pm, respectively) are about 10 pm longer than the sum of the van der Waals radii
(rMvo>w + rNvnw> which are 315, 29S. and 295 pm, respectively (see Table 8.1). The
Fig. 12.36 Effect o( orbital occupancy on mellll- nilrot;en distances. Upper pan of diasrnm t
the M-N 7 distancea (shown a s
The lone pllir o( the ter'liory ornine atom (N 7) is
directed at the a 1 orbital on the meJnl ion. The lower purl of the di118J11m gives the M-N,
and M-N1 weighted mean bond distonc:es. The imine and pyridine nitrogen atoms are
directed at the 2e oftilals on the metal ion. The distances (shown as A) Cor imine nitrogen - ,
atoms, N 1 are slightly shorter and thus are located just below the values (shown as 0) for
pyridine nitrogen atoms. N 1 Dashed lines (-l represent a constunt elcc:tron configuration, .-.
while the dotted line( .... , represents an increasing number of elec:1rons in o given type of 'I
otbiWJ on the metal ion. The orbillll occ:upancy. (o 1)'(
is given under each metal ion
a .t. y. : . [Modiflc:d from Kirchner. R. M.: Meolli. C.; Bailey. M.; Howe. N.; Torrec. L. P.;
Wii"'n. L. J.; Andrew, L. C.: Rose. N.J.; Linsufclter. E. C. CmwJ. Clr<m. R. 1987. 77,
89-16). Reproduced with
>.
- w,>,
!l<r
O<billll
OC<U(>If\C)'
Mn>
f<:l+
4'
II'
1.2.2
2.4.0
co:
-"
l exl
,,,.
--- --- ---:u>>

cu>
d'
4"
2.4.2
2.4.3
:znl
2.4.4
other six M-N bond distances (201-223 pm) ore

shorter than the van
der Wonls radii (an X-Y distance less than the van der Waals sum is often the
accepted criterion for bonding). In spite of constraints that would be expected to
restrict the movement of N 7 away from the metal, it appears that for most of these
complexes, t.he M- N7 distance is too long to be a true bond. For Mn(ll) and Co(II),
the M-N7 distances are shorter than the van der Waals interactions , implying a weak
bond. This is not an unexpected result for high spin Mn( ll) because the a1 orbital is
only half-filled. In the case ofCo{ll), it hos been argued thot the a 1 and I t' levels have
been interchanged, resulting in just
electron in the a, orbital in this complex as
well .
At the same time the bond angles (C- N- C) at the N7 position vary from 112"
(-sr as expected for an amine ligand) in the manganese complex (where repulsion is
least) up to a maximum value of 120" in the iron complex with maximum repulsions.
The tertiary amine nitrogen atom (N7) corresponds to a threeribbed umbrella that has
been inverted by the wind (the handle is the lone pair directed at the meaal). As the a1
and le levels fill, the repulsions increase, the metal-nitrogen distance increases, and
the umbrella begins to flatten:
112
c c c
('y. y/ \
N(7)
,..c
-
C-N(7) \
r I'c
M
(12.9)
Although both geometrical and optical isomerism are in principle possible in

severKOOrdinate complexes, no
ore known . Note, for example, thot the
py,tren complexes must be optically active (see Fig. 12.3.5b). subject of course to
kinetic stability wiah respect to racemiz:Jtion.
Coordina tion
Number 865
Although coordination number 8 c-.mnot bo! rell'JnlcJ as common. the number of

known compounds has increased r.apillly in rccena yeurs. so that it is now exceeded
only by four- and six-coordination. The ractnrs importnnt in this
can be
traceJ largely to improved three-dimensional X-ray techniques and to increased interest in the coordination dlemistry of lanthanide and acainiJe clements (see Chapter 14).
T wo fucaors are imponant in favoring eight-coorllination. One is the size of the
metal cation. It must be sufficiently large to accommodate eight ligands without undue
crowding. Relatively few eight-coordinate complexes are known for the first transition
series. The largest numbers or this type of complex are found for the lanthanides and
actinides. and it is fairly common ror zirconium, hafnium, niobium, tantalum, molybdenum, and tungsten . A corollary is the requirement that the ligands be relatively
small and electronegative. The commonestligaling atoms are carbon, nitrosen. oxygen, and fluorine. The second factor is the oxidation $111le of the metal. a high formal
.., Kepert. 0 . L In C0mp'thmsiw CoorJIMtiun C!wmutry; Wilkinson. G.: Gillard, R. D. McCieva1y, J. A.. Eels.; Perpmon: Oxronl. 1937; Vol . I, PI> 8J..9S.
508
12 Coordination Ch emistry: S!"'etvr e

I
oxidation state favoring eight-coordination. ]his requirement ari.ses out of the elec:troneutrality principle. The formation of eight dative u bonds to a metal in a low
oxidation state would result in excess electron density on the metal. The common
oxidation states are thus +3 or greater. resulting in electron configurations with few
remaining d electrons such as <f. d 1, d2 .64
There are several coordination polyhedra available for eight-coordination. The
most regular, the cube, is almost never found in discrete complexes but occurs in
lattices such as CsCI.67 The two common structures are the trigonal dodecahedron
(Fig. 12.37a) and the square antiprism (Fig. 12.37b). Both may be considered to be
distonions of the simple cube resulling in reduced ligand-ligand repulsions. Tile
square antiprism has slightly less ligand-ligand repulsion than the dodecahedron.
Other geometries are known. but these two are the most important.
From a valence bond point of view. the formation of both the dodecahedron and
the square antiprism can arise from sp'd hybridization. The necessity of using four d
o.
o
o,d
Fig. 12.37 DiSJonions o(

1hc cube to fonn: (a) lllc
trigonal dodecahedron: Jb)
lbe square an1iprism. No1e
lllc similllrity o( the
dodcc:'lhcdron. viewed
down the puckered CDHG
face (C1 axis) and the
anliprism. viewed down 1hc
ABCD 113c:e (Sraxis). [From
Lippard. S. J. Prog. /noTf.
1968. 8. 109-193.
Reproduced with
permission.)
c,
11
tbl
""The pic lure oC the formation oC. for uample.IMotCN>.t-. an

oC Mo' !d'J + sC:r
has litlle physical meaning and is merely a bookkeeping devXc. but h:>rdly more so th:>n Co> +
6NH, disCUSSed extensively e:>rlicr.
There appc::li'S to be alle&SI one cxccplion 10 the Cncr:>l "'lc: (EI4NJ.(U(NCSM has wbic: :>nioos in
she solid. buc thai s1ruc:1ure is no1
in solution tCounlr)'man. R.; McDonald. R. S . l.lltf><g.
Nuc:l. Orrm. t971.J]. 2213-2220). Nole thai lhecube u a sP<cialc:l.!e of the square
like
lllc trigonal prism will1 respect 10 the octahedron. lllc

pared to the squan: antiprism.
interaction> are
com-
High.,. Coor oli11atio11 Numbers
o,.
(g. x :, y r)
o,.
- -- ll:c. nl
509
Fig. 12.38 Eneray level

l;ryl
- - (xr . yr )
for riaht
t oonfin:ltion: {a) wbic (04);
(b) square antiprismatic
(D..,); (c) dodec:ahedr.ll
(D!.I). (From Burdett. J. K.;
Hoffmann, R.; Fay, R. C.
fnorg.
1978. 17.
2.SSJ- ll68. Rcpcoduced
with pcnnissi011.)
(I
(bJ
t<l
orbitals in the hybrid ization for lhe ligand bond ing rationalizes the common occurrence of .fl. d t, and d! conligllr.ltions from a vale nce bond model. Crystal field theory
and molecular orbital theory give a similar picture in that both Jhe square antiprism
and dodec:Utedron give a nondegcnerote lower level (to accept lhe one o r two d
electrons) :md the remaining four metal d orbit:Us (or molecubr orbitals derived
principally from metal J orbitals) lie ar higher levels (fig. 12.18). The LFS Es of both
structures are comparable, and the choice between the t wo is a delicate balance oi
forces. as was the c:lSe for five-coordin:llion. Altho ugh I here is no completely satisiactory treaJment of lhe problem of proper ""lection of geometry for eight..:oordination.
both VB and MO colcul:ltions can correctly predict adjustments of a few degrees
depending upon the electron ron figuration of the met:ll.""
There are extensive possibilities for the formation of geometric :md optical isomers in eight-coordinate complexes. Thus far . apparently only one pair has been
completely charact erized . The d islyme [ dit:! me tho.'lyethylle!her) adduct of samarium iodide. Sm i:(OCCH:CH:OCH 1):1:!. has been isolated in both c is and trans
forms. The trJ ns complex (Fig. 12 .393) has a ccnler of symmetry. Thus. the 1-Sm-1
angle is exactly 180". and the molecule is a bicapped uigonal anuprism. T he cis isomer
(Fig. 1:!.39bl has the lower symmetry oi tlistone.J dodecahedron with 1-Sm-1
of 92".b9
Hig her Coordinatio n

N u m b e rs70
There are few structures known with coordination numbers larger chan 8. The existence of coordination number 12 in some crystal lallices was menlioned above. DiscreJe nine<oordinate structures :1re known fo r a>mplexes suc h as
and
for Jhe hydride complexes [MH.,.f- (where M Tc or Re). These struc tures are
formed by adding a ligand Jo each of the rectangular faces of :1 trigonal prism (Fig.
12 .40).
.. Bun!tu. J. K.:
R.; F.>y, R. C..
Clwm. IP7S. /7, 2SH- l.'68. :.lingos. 0 . M. P. ;
Zhcnyang. L SlruCI. Bondin8 IBttfU.) tll90. 12. 94-93.
60 Sen. A.; Ow:bolu. V.: Rhei,.old. A. L /nort.
1987.26. 1811- 10 .
C4)()rd/nDiion Clotmlnry; Wilkinson, C. Cilbt11, R. 0_ Mc.,. Kepcn . 0 . l . In
CicYCr1}'. J. A.. E<H.: Ptrpmon: Oaford. 1937; VOl. I. pp 9.S.JOI.
510
12Coonllnation Ch-iall'y: Strvcture
(1 )
(b)
Fig. 12.39 Stereoviews oC the structure of (a) lrans-Smi2{()(CH,CH:OCH,):h and (b) cisSmi,{()(CH,CH,pcH,),h. [From Sen. A.; CheboiU, V.; Rheinsold. A. L.lnorg.
1987, 26, t82t-t823. Reproduced with permission.)
Fig. 12.40 Molecular

slrUCturc of the IReH,ranion. IFrom Abr1>hums, S.
C .; Ginsbo:rg, A. P.: Knox.
K. IM'1/. cr,,. &964. J.
permission.I
No compounds are known with ten or more distinct ligands [i.e., nonchelate
structures); however. a few tencoordinllle chelate structures have been described.
One possible structure is a "double trigonal bipyramid" with bidentate nitrate or
carbonate ions at each of the TOP sites [Fig. 12.41a). Coordination numbers as high as
t2 are also known with six bidentate nitrate ligands along the edges of a
dcxlecahedron. but these
are rare (Fig. 12.41b).
G..,eralizationa about Coo<dinoti011 Numhen
511
(a)
fig. 12.41 (a) Structure of the pentanilratocerute(lll) anion. Each nitrate ion may be thought or as occupying an apex of 11
triaonal bipyramid. The resulting coordinntion number is 10 since e11ch nilrate ion is bidentate. The view is down the
principal axis of the triaonal bipyramid 11nd the axial nirrogen atoms as well as rhe cenrral cerium utom are partially
obscured. (b) Structure of the hexanilraroceratelllll 11nion. Each nitrate lipnd bidentare to give" coordination number or
12. (From AI K:>raghouli. A. R.; Wood. J . S.
Commun. 1970. t35-ll6. Beineke. T. A. ; Delj:audio. J . lnurfl. Ch,m.
1968. 7. 71s-n1. Reproduced with pennission.J
Generalizations
about Coordination
Numbers
What generuliutions can be made concerning high and low coonlination numbers? All
have
bul we can list lhc following trends. The factors
favoring low coordination number are:
I. Suji lil(muls und m('tu/s in low u.nJutir>n state.<.
Elcclronically. these will

favor low coordinalion numbers because extensive rr bonding will compensate
in part for lhc absence of addi1ional (potcnliall u bonding. Metals in low
oxidalion slalcs arc ekctron rich and do nol
addiaional contributions of
electron ,Jcnsily from additional lig:tnds.
2. Largl!. bulky li}ltllfd.<. If the: complex is coonlinarivcly unsalur:lled (in an

clc:ctronic sensei. lhen steric hindrance may prc:vcnt additional ligands from
coordiiWiing lo the metal.
3. Cc>llntl!ri<ms of/ow basicity. Any cationic complex with a low coordination

number is a Lewis acid potentially susceptible to attack and coordination by its
anionic coumerion. For this reason. anions of low basicity and coordinating
al>ility are chosen for coomerions. Among the: oxyanions. nitr3te and perchlor,l[c have a long history of use. Doth show some coordinating ability Ccf. the
nitrate complexes discussed in the proceding section). and as strong oxidilers
their presence with organic ligands can be potentially hazardous. The trillate
anion. CF)OSOZ obviates the explosive hazard and also reduces the tendency
toward rotational disorder in crystals. Auoride adducts of strong Lewis Huoro
acids such as BF:;'. Pf6, and SbF6 are frequently chosen as counterions be-
512
12Coordinotion Chetaistry: Slnleture
cause they have a low tendency to trans:fer fluoride ions to the acidic
though such transfer can occur if the catiou is sufficiently acidic. Fn.- ,.v,,....;
often a successful way of abstracting a chloride ion from the
sphere of a metal is to allow t he complex ;w react with silver tetorallunornh-:
Silver chloride is precipitated, and the low bnsicity and
dinating OF; is introduced ns a coumterion. Thus, pot:entially,
butylpyrazolyl)hydroboratochlorocobaltJDJ) could react with silver
borate to give the very stnble silver chlorUde nnd the tetrafluoroborate
three-coordinate cation. However, when
renction was allempted,
abstraction (from BF;) was found insteaod (Fig. 12.42).11
Similar three<oorcJjnate "tripod" l igands are known of
(C(R2 PY>,r (where Y can be 0, S, or a pair of electrons on the
atoms).n These tripod ligands strongly determine three CO<)rdinat:ion
in a pyramidal arrangement, leading to a. fourth coordination by a
Bridging by fluorides may also occur . For example Sbf6may coc>rdinar"
the very strong Lewis acid SbF, to
(F,Sb - F-SbF,r (see
3.42), but it is very dif!kult to abstract a fluorid e ion from SbF;. It
suggested that
should be the amion of choice in the
reactive yet potentially isolable cationic Lewis acids.n
Factors favoring high coordination numbers a.re:
t. High oridaJion states and hard ligands. These will serve to mllllimil.e
electrostatic contri bution to stabilizing tbe complexes. Because d their
electronegativity, fluoride and oxygen-containing ligands can stabilize
oxidntion states.
Fig. 12.2 Reaction of tris(3tbuaylpyrazolyl)hydroboratochlorocobalt(ll) with silver aearalluorobor.lte. A fluoride ion

been abstracted from the BF4 anion to give uia(3-t-butylpyrazolyt)hydroboratoftuorooobah(IO. Ad of the unlabeled
are carbons and ahe hydrogen aaoms are not shown. [Modified from OorreU, I. B. ; P3rtin, 0. lntNg.
1990, 29,
24$2-24$6. Reprodud with pumjasion.)
71 Gordl. I. 8 .: Par1cin. G. trwrr. CNm. 1990. 19,

n Grim. S . 0 .: Smith. P. H.; Nitaolo, S .; Ammon, H. L.: Satelc, L. C.; Sanaolcoya. S. A.;
R. K.: Colquhoun. I. 1.; McFal1..,.. W.; Holden. J. R. , _ ,. Cltlm . .t9SS, U, 2889-lm.
0 .; Sqolcoya. S. A.: Colquboon. I. J.; McFIIfiMie. W.: Khan a. R. K. lnwr. CNm.
2699-2"104.
n Honeychuclc. R. V.; Hersh, W. H. lnort. Ch,m . 21, 21169-2886.
lil<ag lsomMiarn
2. Smo./1 .rttric
well.
of
513
ligands. Agnin, fluorine and oxygen serve
.--3. Large, nonacidic cations. Even though the metals are usually in high oxidation states, the large number of negative fluoride ions, oxide ions, alkoxide
ions, etc., tend to make these complexes anionic o verall. Since high coordination numbers will tend to make large ions, even with small ligands, large
cationic counterions will tend to stabilize the crystal lattice (see Chapter 8).
are to be avoided since they will
Also, small, polarizing cations such as
have a tendency to polariz.e the anion and abstract a fluoride or oxide ion (see
Chapter 4).
In addition to the geometric and optical isomerisl!l discussed previously, there is

another type that is important in inorganic chemistry. II deals with ligands having two
potentially l.ipting atoms that are capable of bonding through one type of donor atom
in one situation but a different donor atom in another complex. The llrst example of
this type of isomerism was provided by h!rgensen , Werner' s contemporary. His
method of preparation was as follows:7
[Co(NH,l,0]CI2
"Solution A"
(U.JO)
..Solution A'. w-1ot..w ((NH,),CoONO)Ciz red
(U.U)
"Solution A"
(U. Il)
HO
[(NH,)3CoNO:JC12 yellow
Jjilrgensen and Werner agreed that the difference between the two isomers resides in
the linkage of the NO, group to the cobalt. TheN-bonded (or nitro') structure was
assigned to the yelloW isomer and the 0-bonded (or " niuito") structure to the red
isomer on the basis of the color of similar compounds." For example, both the
hexaammine and tris(ethylenediamine) complexes of cobalt (assuredly N-bonded) are
yellow, and the aquapentaammine and nitratopentaammine complexes, containing one
oxygen atom and five nitrogen atoms in the coordination sphere. are red. Thus long
before the electronic explanation of spectra had evolved, the correct assignment of
structure was made on the basis of color.
In the following years, these compounds were the subject of considerable controversy. A brief history of the disputing claims is given here both because it indicates some of the methods applicable in such studies, and also because it indicates
the errors that can be perpetuated if reports in the literature are accepted uncritically.
The red isomer is less stable than the yellow isomer and is slowly converted to the latter on standing or more rapid ly by heating or addition of hydrochloric acid to a
solution. Piutu<6 claimed that the absorption spectra of the two forms were identical:
S, 168. Ac:IUIIly lhe IWO Isomers date bDdc much funher:

Gibbs, W.;Gauh, f . A.Am. J. Sd. IIS1,24,86. See Kal6man, G. &. Coord. Chlm. Rn-. tm./1,
,. JtkJensen. S. M. Z. Anor,. Owm.
t6t-t88.
n From wbal you know,,_., olmoel one hundred ye.rs lalcr, W&J '""'a aood or a bad assumption?
76
PiuJti, A. &r. DnA. Owm. Grs. 1911, 4S,
tan.
This was disputed by Shibau.n who claimed that they had quite different spectra!
Lecompte and Duval compared the X-ray powder pall ems of the two forms and found
that they were "rigorously identical ."71 They suggested that the red color in the
supposed nitrito complex was a result of some unreacted starting material. namely
[Co(NHj),O]CI2, in the product .
Adell79 measured the rate of conversion of the red fo rm to the yellow form
photometrically and found it to be a lint-order reaction. This is to be expected if the
conversion is an intramolecular rearrangement invo lving no other species (with the
possible exception of the solvent). On the o ther hand, if the red isomer is actually
unreacted starting material in the form of [Co{NH1),CI)CI2 , t.h e reaction might be
expected to be second order:
(12.13)
(12.14)1!0
Murmann and Taubcll showed that the formation of the nitrito complex occun
without the rupture of the Co-O bond. They used 180-labcled [(N H 1)sCo0H]2 + as a
starting material and found that aD of the 1'o remained in the complex. This argues in
favor of reaction 12. IS in preference to 12. I 6:
1
[(NHJ),Co ac>HJH
(NH,)sCo
N10 1
'0- H
1 1
0 - N-
ONO
((NH 1)sCo11QN0]2 +
1
[(NH,),Co S0H)
+ NOi
---+
]2+ -
[(NH3),CoN02
)2 +
(12. 15)1'2
+ HONO
+ 110 H-
(12.16)82
The labeled nitrite complex may be causc:d to rearrange by heating. In this process
no loss of 18 0 is found even in the presence of excess nitrite, confirming Adell's
hypothesis that the reaction is an intramolecular rearrongement:
"O
[
77
N- 0
I( NH,)5 CoN0 1"01!+ (12.17)
Shibel:l. Y. J. Coli. Sci. Imp. Um. Tul<.vu 1915. JT. t$
.,. Lec:ompte, J .; Duval. C . Bull. Su<. Clrim. 1945. /2. 678. Powder JlOikm.S arc delermined by the type
or c.r yslallatlice and by the spacina.s in I he buice. ll>cy ore U$dul u "finaerprin1i1111" devices for
1hc idcntiliauioro rl c.r ystals .
zn .
.,.. Adell. 8 . Z . AnnrJ:. ChmL Ill#, V2,

.., Finl-otder kinc1ics is 10 be
for an
rcac1ioro. bu1
prescncc i no1 prun{
1hal ""' tuelion lAcs place by such a
The bnckclll in this
rcpreocnl lhc
conccnJr:llions of lhc various species lin mol L- , r:uhC'r lhan indianiuns of Slruclunll moielies.
o1 Murmann. R. K.; Taube. H. J . Am. Chm>. s.rc.
76.
.
., 1l>c clill'erences in thcx IUC:Iions or N,.OJ venus NO;. lhe presence or :lbscnce or OH - as a
procklcl. CIC .. arc rnorc apt)&rcnllhan rc:11 since lhe<e species will inler.>Ct wilh CIC.h Olhet 10 fonn
an equilibrium mixl.urc. n.c aen::nl arswncn1 does no1 depend
lhe euct
rllhc
and products..
linkage Isomerism
Finally, the
isomer:
515
15
0 can be qll:lntil:ltively removed by the basic hydrolysis of the nitro

(12.18)
All these experimems are consistent with the original hypothesis of J(6rgensen and
Werner of linkage isomerism. It is difficult to rationalize the "rigorous" contrary
evidence of some of the early wort<ers except by the general phenomenon that it is
deceptively easy to obtain the experimental results that one expects and desires.
Werner knew of two other examples of linkage isomerism. both nitro-nitrite
isomers, and they underwent the same period of skepticism and confirmation as the
compounds discussed above although considerably less worit was done with them. A
period of more than SO years passed before Basolo and coworkers attacked the
problem with rather amazing resultsJ>l Linknge isomerism, once relegated to a few
lines as an "exceptional" situation in discussions of isomerism, now boasts an
extensive chemistry which continues to develop. The first new linkage isomers prepared were nitro-nilrito isomers of Cr(lll), Rh(l ll), lr(UI), and PIC IV). ln all cases
except Cr(IU). the nitrito isomer converts resdily to the more stable nitro isomer.
Electronic Effects
The first thiocyanate linkage isomers were isolated after it was noled lh.at the structures of cis complexes containing thiocy:mate and either ammonia or phosphine were
S. or N-linked. respectively (Fig. 12.43). The hypothesis provided was that these
isomers were more sl:lble than the alternatives (i.e., S.bonded in the phosphine
complex, N-bonded in the ammine complex) because of the competition for., bonding
orbitals on the metal. The phosphine forms the best ., bonds and hence tends to
monopolize the -;r bonding d orbitals of the plutinum. reducing the stability of the
weaker sulfur rr bond, hence the thiocyanate ion bonds through the nitrogen atom. In
the absence of competition for., orbitals (ammonin cannot form a .,. bond). the sulfur
atom preferentially bonded. Using this hypothesis as u basis. Basolo and cowork
ersK4 attempted to find complexes in which the .,. bonding tendencies were balanced,
Fig. 12.43 Strw::turcs or IPt(SCN):(NH,h) and tPtCNCS):,<PR,h l illustr.uina the competitiooo

for .,. bolllline d orbitab oil he mc1:11. One set of" bonds hus been omiucd for clurity. The
..d
.. lcR-righa symmetry
been luSJ due lu pobriz:,tiun. Compare with Fig. 11.30.
In addition lo empty d orbilllls. su1rur h:llltilled p ort>imls. See T:.blc 11 . 11 Dnd uccompanying
diSOJs.ion.
"'Ba501o. F.; H:mvnaker, G. S. J. Am. CNm. St>t'. '"' 82.

ln"'11
1961. 1. 1-S.
"' Bascllo. F.: Burmcister, J. L. ; Poi!, A. J. J. Am. Clltm. Sac-. t96J,8.$, t71)()-171l l. Burmcisau. J. t...;
Basolo. F. lmJrK. cm. 196-C. J, tS87-tS9l.
51 6
12 Coord i -i011 Chemistry: Slnlcture
allowing the isolation of both isomers. Examples of the complexes thus isolated are
[(Ph,AshPd(NCS)2), and [(bpy)Pd(SCN)z), [(bpy)Pd(NCS)z). In
both cases, on warming, the S-bonded isomer is converted to the N-bonded isomer ,
which is presumably slightly more stable.
The competition for 1T bonding is indicated in the behavior of the selenocyanate
group, SeeN-. This group readily bonds to the heavier group VUIB (8) metals via the
selenium atom to form complexes such as [Pd(SeCN)J1 - and rran.r-[Rh(PPh3)z(SeCNJ2r . However, in a closely related complex, rran.r-{Rh(PPh3)z(CO)(NCSe)), the
presence of a trans carbonyl group apparently favors coordination via the non-1Tbonding nitrogen atom. as
Another example of apparent electronic (i.e., 1T bonding) control of linlcage
isomerism comes from bidentate chelates having one strong and one weak donor atom
(f"18. 12.44). The presence of an 5-bonded thiocyanato group trans to the non-1Tbonding nitrogen atom, but an N-bonded isothiocyanato group trans to the ., bonding
phosphine donor is indicative of 1r competition in this complex.l6
Steric Effects
Sterle factors may play an important role in stabilizing one or the other of a pair of
linkage isomers. Thus
and
isoselenocyannto pairs differ in steric requirements
12.4S).
One or more factors may be operating simultaneously to provide a delicate
balance of counterpoising effects. An interesting series of compounds illustrates the
competing effects in linbge isomers of square planar palladium(O) complexes
(Fig. 12.46a-d).87 The six-membered chelate ring in rlf!llre 12.46c allows an essen-
F"lg. 12.44 The molecular

structure or i..,chiocyanak>lhiocyanatO(l-diphenylphosphino-3-dimcthylaminopropane)palladium(ll).
Note: (I) trans ananaemcnl
or P- Pd-N and
N- Pd-S bonds and (21
tinear vs. bent anansement
or the NCS JfOOp. [From
Meek. D. W.; Nicpon,
P. E.: Meek. V. I. J . Am.
Clttm. Soc. 1970. 92.
$l$l- S3.S9. Reproduced
with permission. }
IS
16
Burmeisler. J. L. ; DeStefano. N. J. C/wm. Comnum. tt?O, 1968.
Meek. D. W.:
Palenik. G. J.
P. E. : Medc. V. I. J. Am.
trmr. Clwm. t970. 9. 2754-2160.
Soc. lf70. 92. $3$1-Sl$9. Clark. G. R.;
., P*nik. G. J .;SIIdfetl. W. L.; Mathew, M.: U. M.: Medc. 0. W . lnorr. Nuc/. CMm. ull. 1914.10.
12.5-128.
l.inlcoge loomeri-
511
F;g. 12.45 Sleric

requir<mems or
ambiclentate
Note
that the aflgles marked a
are larger than those
marked fJ. In addition. the
van der Waala radii of S
and Se are larger thD.n that
N. (In computing the
angles a and fJ quanti
tatively. the van der Waals
radii or the terminal 0 lind
N would have to be
(a)
_,.---
--D)
M@
or
J"
........ _
Jl-0
included.)
N
(b)
I'll'. . . . ,..--;6,;;:---,.......c
/Ph
236.6/ ' \236.4
(b)
(a)
c-c-c
Ph
............ ,
B9.t
N
(c)
c-c-c
CH,. . . . ___,
\/Ph
92.4
20Sy "'229.S
N
(d)
Fig. 12.46 Strucrures or four palladium complexes iRustr:uing combined steric: and electronic
ell'ects on bonding of the thiocyanate ligand. [From Palcnik. G. J.; Steffen, W. L .; Matltcw.
M.; Li. M.; Meek. D. W. fnorg. Nucl. CMm. utt. 1914. 10. IZS-128. Reproduced with
permission.)
tially unstrained angle of 89.1 at the palladium atom. The aryl-alkyl-substituted

phosphines are only weakly .,. bonding, but the expected N-bonded isomer obtains. As
the chelate ring is contracted to five atoms (Fig. J2.46b), and then to four atoms
(Fig. 12.46a), the electronic environment on the phosphorus is essentially constant,
but the steric constraints are relaxed as shown by the decreasing P-Pd-P bond
llll81e. First one (Fig. 12.46b), then both (Fig. 12.46a) thiocyanate groups rearrange as
the large sulfur atom is allowed moce room around the palladium atom. However, the
same effect can be accomplished by holding the geometry essentially constant (Fig.
12.46d), if one or the phosphorus atoms is replaoed by a smaller, non-?rbonding
518
12 Coonlinolion Chemistry: Structu,.
nit rosen atom. Rearrangement of one of the thiocyanate ligands occurs. Significantly,
it is the group that is trans to the nitrogen atom that isomerizes. Furthermore, the
ubiquitous presence of the trtms infiumc.311 in these complexes indicates the pervasive consequences of electronic effects. We may therefore conclude that if either
the electronic or the steric factor in a series of complexes is held constant, it is
possible for the other factor to determine the nature of the resulting linkage
Symbiosis
]jilrgensen90 proposed the principle of symbiosis with respect to hard and son
acid-base behavior. This rule of thumb states that hard species will tend to increase
the hardness of the atom to which they are bound and thus increase its tendency to
attract more hard species. Conversely, the presence of some soft ligands enhances the
ability of the central atom to accept other soft ligands. In terms of the electrosllltic
versus covalent picture of Pearson's hard and soft or Drago's ,.0 and C"C8
parameters (see Chapter 9), the best "strategy" of a complex is to "put all its eggs in
one basket," i.e., form all hard ("electrosllltic") or all son ("covalent") bonds to
ligands. There are many examples that could be given to illustrate this tendency in
metal complexes:
All ligands lwrd
All ligands soft
(Co(NH 3)_,NCSf"
[Rh(NH3)_,NCSf"
[Fe(NCSe)J2 -
[Co<CN)s8CNJ'[CpFetCO)z(SeCN))
In the first example the hard ammonia ligands tend to harden the cobalt. and so the
thiocyanate bonds preferentially through the nitrogen atom. Conversely, the soft
cyanide ligands soften the cobalt, making it bond to the son end of the thiocyanate (the
sulfu r atom). Similarly, in the case of Rh(lll) live ammonia ligands result in preference
for nitrogen at the sixth position; if all six soft sulfur atoms can ligate, they will.
Iron(! I) appears to prefer the hard nitrogen atom unless softened by the presence of
carbonyl groups.
The symbiotic theory adequately covers most of the linkage preferences observed
for octahcdntl complexes. Unfortunately, it contrJdicts exactly the -rr bonding theory
applieu above to square planllr complexes. Pi bonding cru1 be equated with softness. u
bonding with hardness. In the case of octahedral complexes we say that the presence
of soft, -rr bonding ligands favors the addition of more son, -rr bonding ligands (symbi
otic theory), but in the case of square planar complexes we say thut soft. -rr bonding
ligands discourage the presence of other -rr bonders and favor the addition of hard.
u-only ligands (,. competition theory). Obviously t he situation is somewhat Jess than
perfect if the two theories are applicable only in limited areas and appear to contradict
each other in their basic raisons d'etre. Nevertheless they have heuristic value and
""See Cbnpter t3 for a di.cusaioo of the etectromc fac1ors openllivc in t he trlln.< innuc:ncc .
.. See Meek. D. W.; Nicpon. P. E.; Meek, V. I. J. Am. Cftm. Sf)c. 1970. 92. l3SI- S359. Huhcey.
J. E.; Grim. S. 0 . I
N11cl. CIH!m. utt. 1974, 10.973-975. The>c: J'l'PC" nn:>lyzc the clrclronic:
and su:ric fllCiors in compounds of this type.
90 Jt&rgcnsen, C. K. lnorr. Chm. 1964. J. t201-t202.
l.ink nge Isomerism
519
serve to emphasize that there are many factors involved. both electronic and steric. in
determining which of the possible isomers will be preferred.va
Pearson. in elaborating upon these
dist illed the essence of the .,. competition theory to two soft lfgands in muwul trans posirions will laave u destabilizing
injfrrenu on eaclr otlru wlren tltltlched to class (b} (soft) metal atoms. He also
provided additional examples of the rule that symbiosis prevails in octahedral com
plexes. antisymbiosis in square planar complexes. Tetrahedral complexes are expected to show antisymbiosis but on a much reduced scale compared with the square
planar complexes.lll
Prussia n Blue ond

Rela ted Structures
Linkage isomerism is but a special case of ambidentate behavior in ligands. The

cy.mide ion provides good examples of such behavior. In discrete complexes it almost
always bonds through the carbon atom because of ahe stronger .,. bonding in
that mode. II has also been reported to form a few linkage isomers such as
cis-[Co(trien)(CNl1 ]+ and cis-{Co(tricn)(NCJ:!t.
A large number of polymeric complexes is known containing ambidentate cyanide
bridging groups. These are related to .. Prussiun blue. which is formed by the addition
of ferric salts to ferrocyanides :
Fe>+ + [Fe11!CN!J"- -
Fe4 (Fe(CNlhh
(12.19)
Addition of ferrous salts to ferricyanides proc.luces ..Turnbull's blue":

Fe1 + [Fc! 111(CNlhl1 -
FcJFC(CNlhh
(12.20)
It has been shown that the iron-c:yani<Je frnmework is the same in !'russian blue,
Tumbutrs blue. and other related polymeric cyanide comple:tes rfig. 12 .47), differing
only in the number of ions neces.'IUry to maintain electrical neutrality. Variou5 quantities of w-.ller molecules may also be present in the large cubic holes . Prussian blue
has u strucaure wiah hexacuordinate. low spin Fe( II) bonded through the carbon ruoms
and hexacoordinnte. high spin Fetl ll l
through the nitrogen atoms of the
cyanide. To achieve this stoichiometry. one-fourth of the Fe( I [) sites are occupied by
waaer molecules. This reduCI:) the number of bridging cyanide groups
(fe11 -C:;:;;N-Fe111 ) somewh:ot. and water molecules occupy the otherwise empty
ligantl pusitions
created. Then: is als.> one water molecul.: in e;och cubic sile.9l
prepared from dill'crcna
m:ucriuls ,
blue is identical.
X-my anti magnetic d:ua suppolrt ahis idcmit y.the best evidence comes rrom
the fact that the Mosshaucr spectr:t of Prussian blue and Turnbull's blue are the
sotme."" Since Mllssoouer spectr;t are ex tremely Sc!nsitive to the electron density and
'" FOf' rurthcr di>cusr.ioo cf ahis problem. >
N. J .;
J . L lnt"1:. Chrm. 197t.
10. 99!HOOJ. h >hould
be notetl rllaa ullhoualt lht/Hiti!(Untnrm ohymbiosi is very real. ahe
choice or lhc word symbio;;s lo dc:!i<>ribc it ill uni'Or1UNIIC. A$ DcStcranu and IJIIrnlCislcr poinl OUI.
syllfhlusis in biclogy rd'cn 10 lhe
lq,"Cihcr" or
/>C'<'its. r.uher llllln Ihe same
spe.C.. in inlirnaJc
Ncvenhdcu inart-tnic
wil unclolA:llcdty conainuc 10 use
lhc aerm in its currc.nJ .M:nse..
: Pe""""' R. G. INTJI. C'IJm. 197l. /J. 712-713.

)
H. J.:
0 .; P<Ucr. W.: l.udi. A. lnoT]I. Chc-m. tffl. 16. 2'1U4-27t0.
.. Ourx=. J. F.: Widoy. P. W. R. J. Chtm. S.>t:. 1963. t l20-tt:U. Fluck. E.; l<.crla'. W.; Nwwinb.
w. A.,e,..... ChtM. lm. 11. &ltl. t96J .?. 277-217. Bonneue. A. K .. Jr.: Allm. J. F. lrHWJt. Cum.
1971. /0, t6t3-lhll>. 1ltc method or prcp:n:uonn nd preciP<IIIIJUn rllilY all'l lhe mlure oC lhe
prccipiloae CcollcidDt. cac.t and so.,.,.,.... amounl5 d waaer and C&lions rroy be inc:orpor:!led in lite
Slnldure..
520
12 c -rdinatian Chetaistry: Stn.c:ture
Fig. 12.47 Portion of the crystal $1Nc:nwe o1 Pru&Sian blue sbowinalhe bridcina by
ambidentate cyenide ions. Circla represent iron( II)(()), iron(lll) (0), and oxyaen in wa1er
ce1. remainina intcrsliti21 or zeolilic" water in the aJbic sites bu been omncd for
clarity, as have mo51 ol the cyanide ions. In addition, some cl the cyanide ions are replaced
by
molecule$ c:oordinaled to iron(lll). and 1here arc also vocancics in die: struaurc.
[Modified l'rom Buser , H. J.; Scllwanenbacll. D.; Peucr. W.; Lu4i, A. / norg.
1m.
16,
Reproduced with permission.)
microenvironment ob0t1t the iron atoms. this confirms the identity. Ferric ferricyanide
(Berlin green) consists of iron(lll) at all iron sites. and white Everitt's soil (actual ly
Kl(Fe1'(CN)6 Fe 11 ]) consists of iron( II) at all iron sites and potassium ions in all of the
interstices.
If one pyrolyles Prussian blue gently in a vacuum or, better, precipitates ferrous
fenicyanide in I he presence of n reducing agent such as potassium iodide or sucrose,
the compound formed is truly iron(II) hexncyanoferrate(111).9S However, it reverts to
Prussian blue rapidly upon warming with dilute hydrochloric acid or standing in humid
air.
A particularly interesting example of linkage isomerism was reported by Shriver
and coworkers.96 Mixing solutions of iron(II) salts and potassium hexacynnochromate(IH) results in n brick-red precipitate which turns dark green on heating:
Fe2 + + K + + [Cr(CN)J3 KFe[Cr(CN)J
11
KFe11[Cr 111(CN)J
11
KCr' (Fe (CN>J
dark green
"Coscr<wc. J. G.; Colins. R. L : Muny. D. S.: J. A.m . Clwm. Sec.

R.; Collins. R. L J. CDOrt!. CMm. IJ74. J. 3D.
brick red
(12.21)
(12.22)
tm. 9$, IOSl-1016. R.obineue.
,. Shri-. D. F.; SMvu, S. A.; Andenon. S. E. lfiO'I. Owm. 1965. 4, 123-130.
Other Typ.. of Jaomllf'im
521
This has been interpreted in terms of linkage isomers of the type:
. .. Fei'-NC-Cr"'-CN-Fel'-NC-0"' . . .
brick rod
. .. Feii-CN- Cr"'-NC-Fell-CN (ll

-
dattt sreen
)
23
in which the linear arrays shown in Eq. 12.23 represent portions of the ctJbic arrays
shown in Fig. 12.47. The initial product is Ccoordinated to the chromium( Ill) since
that was the arrangement in the original hexacynnochromate(lll). The iron(ll) coordj.
IUILes to the nvnilable nitrogen atoms to form the Prussian blue-type structure. As in
the case of Prussian blue discussed nbove, however , there will be preferential LFSE
favoring the coordinntion of the strong field C-linkage to the potential low spin
configuration of iron(II), npproximntely twice as great as thnt of the
configuration
of chromium(lll) (see Table 11.3).
4t
Other Types
of Isomerism
In general the other types of isomerism for coordination compounds are less interesting than those discussed previously, but will be listed briefly to show the variety of
possibilities.
Ligand Isomerism
Since many ligands are org;mic compounds which hove possibilities for isomerism, the
resulting C<Jmplexes can show isomerism from this source. Examples of isomeric
ligands are 1,2-diaminopropane ("propylenedinmine," pn) and 1,3-clinminopropane
("trimethylenediamine, In) o r ortho,
and para-toluidine (CH,C.H4 NH2) .
Ionization Isomerism
The ionization isomers [Co(NH 3),Br]S04 and [Co(NH 3),SOJBr dissolve in water to
yield different ions and thus reoct di!l'erenlly to various reagents:
+ BnH
----+
&S04(s)
(12.24)
+ Bn2"'
[Co(NH,)5Br]S04 + Ag"'
----+
No reaction
(12.25)
[Co(NH 3)5 8r]S04

[Co(NH,),SOJBr
[Co(NH,)5SOJBr
Solvote Isomerism
----+
+ Ag -
No reaction
(12.26)
AgBr(s)
(12.27)
This is a somewhat specinl case of the nbove interchange of ligands involving neutral
solvate molecules. The best known example involves isomers of "chromic chloride
hydrates," of which three are known: [CtiH2 0 )JCI,, [Cr(H 20 ),CI]CizH20, and
[CtiH20)4C12]CI2H20 . These differ in their reactions:
[Cr(H20)JCI,
ddot"....., H,SO,
[Cr(H20),CI]CI2 Hz0
ck...... .... K,SO'
[Cr(H2 0)5CI]CI2
(12.29)
[Cr(H 20)4C12]CI2Hz()
<ldi)'W. -
K,SO,
[Cr(H20 )5CI]CI2
(12.30)
(no change)
+ 3AgCI(s)
[Cr(H20)JCI,
[CtiH 20)J,.
[Cr(H20>,0)CI2
[Cr(H20),cll2
[Cr(H 20)4C I2]CI ---+ [Cr(H20)40:J+
Coordination
Isomerism
2AgCI(s)
+ AgCI(s)
(12.28)
(12.31)
(12.32)
(12.33)
Salts that contain complex cntions and anions may exhibit isomerism through the
interchlmge of ligands between cation and onion. Fo r example, both hexaam-
522
minecOOalt(JIJ) hexacyanochromate(lll), [Co(NH,)J[Cr(CN)J. and its coordination
isomer, [Cr(NH,)J[Co(CN)J, are known. Another example is (Cu(NH,)J[PtCI.J and
[Pt(NH,)J(CuCIJ in which the isomers differ in color (as a result of the d 9 Cu2
chromophore), being violet and green. respectively. There are many cases of this type
of isomerism.
A special case of coordination isomerism has sometimes been given the name
"polymerization isomerism" since the various isomers differ in formula weight from
one another. However, lhe term is unfortunate since polymerillll.ion is normally used
to refer to the reaction in which a monomeric unit builds a larger structure consisting
of repeat.ing units. The isomers in question are represented by compounds such as
[Co(NH,)JN01)z)[Co{NH,)2 (NO:)J,
(Co{NH 3)J[Co(NO..JJ,
[Co(N H3) 5NO:l
[Co(N H3)z(N02)JI, [Co{NH,)J[Co{NH,)2(NO:)J,, [Co(NH,).(NOz)zh[Co{N02)J,
and [Co{NH,),N02J,[Co(N02),)z. These all have the empirical fonnula
Co(N H3h(NOJJ, but they have formula weights that are 2, 2, 3, 4, 4, and S times this,
respectively.
The Chelate
Effect97
Reference has been made previously to the enhanced stability of complexes cxmtaining chelate rings. This extra stability is termed the chelate effect. It is chiefly an
entropy effect common to all chelate systems, but often additional stabiliution results
from enthalpy changes. Entropy changes associated with chelation are complex.9t
With regard to translational entropy there are two points of view which are essentially
equiv31ent in that they are both slatistical and probabilistic in nature. 1lley therefore
rel:ue to the entropy of the sysJem but they look at the problem from somewhat
different aspects. One is simply to consider the difference in dissociation between
ethylenediamine complexes and ammonia complexes, for example, in terms of the
effect of the ethylenediamine ring (the electronic effects of the nitrogen atoms in
ethylenediamine and ammonia are similar). If a molecule of ammonia dissociates from
the complex, it is quickly swept off into the solution, and the probability or its ever
to its former site is remote. On the other hand, if one of the amine groups of
ethylenediamine dissociates from a complex. the ligand is retained by the end still
auached to the metal. The nitrogen atom can move only a few hundred picometers
away and can swing back and allnch to the metal
The complex has a smaller
pmb:tbility of dissociating and is therefore experimentally found to be more stable
toward dissociation.
A more sophisticated approach would be to consider the reaction:
(Ni(NH 3) 6)2+ + 3en :;::= [Ni!en>i + 6NH 3
( J2.34)
in terms of the enthalpy and entropy. Since the bonding characteristics of ammonia
and ethylenediamine are very similaJ"19 we expect t1H for this reaction to be smal l. To
a first approximation the change in entropy would be expected to be proportional to
., Hancock, R. 0 . ; Martdl. A. E. COIMWIIIS lmNR. Clr-. 1911,6. 2.37-284.

"'Oluna. C ...S. J. Chm.
ltl4. 61 . t062- 1064. Mcyen, R. T. lnorg. c.-m. 1971, 17. 9Sl-9S8.
,..,
and ommonia urc olmosl identical in fid<l Slrei\I)N (their I facaors dill"cr by leu
t han
Olaplcr I ll, and so the LFSE rOI' c:omplucs witb the PmC metal ion ,.;u be almotU
idrnaical. Howeva-. clhylenediamiooe is also a
bose than amrn.lllia 11-om the inducti.-e dTcct
of the mclhylcoc aroups. In adclilion there may be cntbalpy .Jill'U'Ct'oCn in the rOITII ol rirc stnin or
Sleric: dJecu.. Sec Table t2.6 anc1 the rolowina discussion.
n. O.lat Effect
523
Tal>lel2.6
th. d.lcft dKtill ca......... af Ncbl(ll) Gild <cw-(11)
Ammoooia
. cam.,&.xes
[Ni(NH,)2(H20 ).f+
[Ni(NH,)4(H20 ) 2)2+
[Ni(NH,)J1+
............
camplues
t.H
li.G
- 29.0
-33
-65
-Sl.8 -100
- 46.3
- 44.7
[Cu(NH,)4(Hz0)z]1 + -74.2
-46
-92
-12 [Nien(H10 ).f

-63 [Ni(eo)z(Hz0)2]2 +
- 163 [Ni(en>,t
CIMial. .w.ct
li.G
t.S
t.H
li.G
-38
- 4 [CUen(HzO>.ll+
- 60.1 -5s
-58 (Cu(enJiHa0)2]2+ -11 1.8 -107
314n
t.H
11 - 12.9 -5
-n.2 -n 12 - 3o.9 - II
.- 101.8 - 117 - 42 -50.0 - 17
- 41.9
2S - J5.S
-8
29 - 37.6 - 15
29 33
74 67
t2t 100
29
88
33
67
Mocificd rrom H8ncock, R. D.; Martdt, A. E. Ccmmtnu lnor1. Chnn. lf8l. 6, 237-284. Free enazy and crnhalpy ct.qaes are e.t
preSICd in u
Entropy ehatwes arc cxpreucd in J mor I K- 1
EnlropiesoCchdatlouhould bec:ompated willl33.4n(n
bucd on li.S nR In 5S.5.
the difference in the number of particles present at the beginning and end of the
reaction. The reaction proceeds to the right with an increase in number of particles.
and hence translational entropy favors the production of the chelate system instead of
the hexaammine complex. too In the replacement of water molecules by chelotes, the
increase in number of molecules in solution causes an increase of entropy given by
liS a nR In 5S.S = 33.4n J mot- K- 1 where n is the number of chelate rings.
contributing 10.0 kJ mot- to the free-energy stobili:c:ation of tho: complex at 300 K
for each chelate ring formed . As seen in Table I 2.6, the calculated entropy values
(33.4n J mol- 1 K - 1) ore in reasonable agreement with the observed values . Given the
complexity of the thennodynamics involved in chelation. it is somewhat fortuitous
thlll this simple approach is ns successful os it is.
There ore also decided enthalpy effects present. These may be most simply
viewed in terms of the chelate being "preformed. In other w0f'd5, certain energy
costs that have to be paid to form complexes. such ns steric interference between two
adjacent unidemote ligands. repulsions between the dipoles of two a<ljocent ligands.
etc . may have been paid. in part, when the potentially bidcnta1e li&and was originally
fonned.and need not be expended again upon complex formntiun. Tu wharever ex tent
that this is true. the cnth:olpy of formation of tho: chelAte will benefit with recard to that
or the uni.Jcnt;uc complex.
finally. chdating ligan.ts such as ac.:tylaceaone enjoy resonance )Wbili:c:otion as a
result of forming six-membered rings having some aromatic chnrdCter. Aceaylacetone
(2.4-pentanedione) coordinates as on anionic enolate ligand:
OH
U
I
CH 3- C -CH=C-CH 3
diketon<
o
Il
enol
(12.lS)
oI
CH 3- C- CH=C-CH 3
..__
r010N1 nco fonns of Ihe cnolote anion
1'"' Eni<OIIY ch1111ges :wocialc4 wino solvalion and rot>lional differences Mre also imponanJ. 1llc:
1
driYin& Coree for this reaction Cli.G -50 kJ mol- 1 comes predominAnlly from lhe Tli.S term.
524
12 CooTdinat;"" Chemis try: Slnletvre
With trivalent metals,

thus forms neutml Iris complexes such as
[Al(acac),j, [Ti(acac),], [Cr(acac) 3], nnd (Co(ncac),J. As a result of resonance, the two
M- 0 bonds in each of these comple)(es are equal in length, as are the two C-0 and
the two ring
bonds, giving a symmetric structure (only one ring shown):
c-c
(12.36)
Ugand-metaJ .,. bonding enhances the delocalization of electrons compared to that in

the free enolate, producing some resonance stnbilization .
An interesting e)(ample of at least partial destruction of reSOClance from
Jahn-Teller distortion is given by
(see
I I .SI and accompanying discussion of the Jahn-Teller effect). As a result c:l
this distortion, the two Cu- 0 distan<:es are not equivalent (197 vs. 230 pm) and
presumably the.,. bonding is not equivale.nt. Therefore one resonance form is favored
over the other, and as a result there is an alternation of bond lengths throughout the
ring (F"I&- 12.48).
The chelate effect is amplified in the case of polydentale ligands that form several rings with a single metal atom. The extreme of this form of stabilization is
found with hexadentate ligands such as ethylenediaminetetraacetate (edta),
COOCCH2)2 NCH2CH 2N(CH 2C00- )2 which has si.x ligating atoms.
We have seen !hal chelate rings obey much the same type of steric requirements
with respect to confonnations as do organic rings. Unlike organic ring systems,
maximum stability in chelate rings usually arises from five-membered rings because
the metal 111om is larger than a carbon atom and the bond angles at the metal
(L.-M-L) will be 90" in square planar and octahedral complexes in contrast to an
optimum angle of IQ9i0 for tetrahedral carbon. For rings exhibiting significant resonance effects, such as
si)(-mcmbered rings are quite stable. Larger
and smaller chelate rings are known, but they are not nearly so stable as the live- and
six-membered species.
Fig. 12.48 Bond leqths in

die accaylaceaonaae ring of
(C\J(py)(hfahJ. [From
Vciclis. M. V.: Schreiber,
G. H.; CouaJI, T. E.;
Palenik, C . J. J . Anr.
t"'
CMm. Soc.
91,
t8S9- 1860. ReprockJccd
wid! permission.!
Th Chelat EHect
Macrocycles101
525
An area of particular research interest in recent years has been the construction of
planar, macrocyclic ligands. These are special types of polydentate ligands in which
the ligating atoms are constrained in a large ring encircling the metal atom. Examples
are polyethers in which the ether oxygen atoms. separated by two methylene groups
each, lie in a nearly planar arrangement about the central metal atom (Fig. 12.49) and
the remainder of the molecule lies in a "crown" arrangement, hence the name "crown
ethers."J02 AU of the oxygen atoms "point" inward toward the metal atom, and these
macrocycles have the unusual property of forming stable complexes with alkali
metals. This exceptional stability has been attributed to the close fitting of the alkali
melal ion into the hole in the center of the ligand. However, some data seem to
contradict this simple model. Although calculations indicate that the l.i + should
preferentially fit crown-4, in solution crown-4, crown-.5, crown-6, and crown-7 all
prefer K + . HancockiOJ has suggested that this may arise because the live-membered
ring formed when any of the above crown ethers binds to an alkali metal cation besr
fits the size of K+.
Gas-phase studies'04 show that crown-S prefers Li+ more than lhe other alkali
metal cations:
crown-5:
u >> Na+ >
K+
> cs
On the other hand crown-6 shows more affinity for Na+ and crown-7 prefers K:
crown-6: Na 2: K+ >
crown-7:
u > Rb+ > cs

u > cs
K+ > Na+ c:: Rb+ >
The difference in affinities shown in gas and solution phases suggests that solvent
effects are quite important. These ligands have the unusual ability to promote the
solubility of alkali salts in organic solvents as a result of the large hydrophobic organic
ring. For example. alkali metals do not normally dissolve in ethers as they do in
ammonia (see Chapter 10), but they will do so if crown ligands are present:
K + crown-6
[K(crown-6)]+ + [e(solvent)J-
(12.37}
The ability to complex and stabilize alkali me1al ions has been exploited several
times 10 effect syntheses that
otherwise be difficult or impossible. Consider the
101 This is an area in which thrtt chemists recently shared the Nobel Prize in chemislry (1987): C. J .
Pedenen (Foocnote t04).J. M. ldln (Footnole 112). and 0 . J . Cram (FOOl note 110). The moterials
ci1ed in lhesercfen:ncesconJain Jheir"Nobellaureateaddresses. See also lzan, R. M.: Pawlak, K.;
Bradshaw, J . S.: Bruening, R. L Clwm. Rhl. 1991. 91. lnl-2085.
to> Pedersen, C. J. Ang<'W. Chrm. lnt. EA.
Eng{. t98S. 27. 1021-1077. The nomenclature orthe organic

rinJ sy$1ems is complex (llle ligand in Fi.s. 12.49 is 1.4.7,10, 13,1f>.hexaoucydoocu>dcanc:). and
Pedersen condensed 1his 10 "18-c:rown-6. in ..tlic:h the numb..- 18 refers to lhe mac:rocydic rins
size. "crown is a 1rivial ge.,..-ic name for the class. ond 6 refers to 1he number of oxyscn a1cms.
This name: is somc:Jimcs further abbrevia1ed 10 18C6 in fonnulas. For purposes or 1he PfC60nl
discussion. the!c compounds may be rererrcd 10 a.s "crown-4," "'crown-S." and "crown-6,'" wilh
lhe implica1M>n 1hat the ring size is e(Jial to lhrec: limes the number or OX}'IIen a1oms. The
eryplanda. 10 be discussed shortly. may be abbreviated 10 lhc poi I or C222, standing (Or "cryptand wi1h 1hree pain oxysen moms on the
the foo1ball'" (sec page SJO).
or
10>
or
Hancack, R. 0 . J . Cllem: Educ. 1992, 69, 615-621; Penf"<lives in Coordination Chtmirtry;

A. F.; Floriani, C.; Mc:tbach, A. E . Eds.: VCH: Weinheim, 1992; pp 129-ISI.
'"' Malcknia . S.; Brodbell, J. J . Am. Clttm. Soc. 1992, 114, 4295-4298.
526
12 Coordination Chemi&try: Structure
fig. 12.49 Strucnm oC 1he macrocyclic: complex oC pOtassium wi1h 18-(;l"owt\-6. The planes
bear a .SO.pm grid and 1he ligh1ing source is a1 inftinily so thai shadow size is meaningful.
This drawing was made wi1h the KANvAS computer graphics program. This program is based
on the program SCHAKAL of E. Ketler (Kris18llographisches lnstitul dcr Universillit Frieburz,
Germany), which was modified by A. J. Arduengo. Ill (E. I. du Pont de Nemours & Co .
Wilminglon, DE) to produce 1he back and shadowed planes.
compound Cs +Au-. Its existence might :u first appear to be improbable since it is an

ionic compound between two metals rather than between a metal ami a nonmetal. Yet
inspection of the ionization energy of cesium and the electron affinity of gold (or
merely comparing the Paulingelectronegativily of gold, 2.54, with that of iodine, 2.66)
spali<s curiosity: It should be investigated. Indeed, based on the suggestion of the late
Sir Ronald Nyholm, the first edition of this book (1972), as well as this edition
(Footnote 4, Chapter 4), both mention the possibility of such a bond. The experimental stumbling block is obvious, however: If you mix two metals, how do you determine
that you do indeed have an ionic compound and not an alloy? When cesium was
allowed to react with gold, the conductivity in the melt was characteristic of an ionic
compound. Further evidence was desirable, however. Two approaches were used.
One was to take advantage d the solubility of alkali metals in liquid ammonia, the
strong reducing power of the free electron. and the stability of reduced species in this
medium. (Note that Au- should be a powerful reductant.) The second was to stabilize
metals. such as SO<lium, that might not otherwise react (recall that the ionization of
any metal, even so<lium or cesium, is
with macrocyclic polyethers to
form [Na(macrocycle) J+Au - salts. A combination of these techniques with physical
The Chelate fffec1
527
methods such as nonaqueous electro<:hemistry and those showing the nnomolously

low ESCA binding energy and the MOssbnuer chemical shift were used to charactesile
the - I gold.IOS Unfortunatdy Sir Ronald did not live to see his prediction verified; he
died in an automobile accident in 1971.
In a similar manner the so-called Zinll salts composed of alkali metal cations and
clusters of metals as anions (see Chapter 16) were known in liquid ammonia solution
but proved to be impossible to isolate: Upon removal of the solvent they reverted to
alloys. Stabilization of the cations by complexation with macrocyclic ligands ollowed
the isolation and determination of the structures of these compounds.
This general trait of cro wn ethers and cryptands (to be discussed later) to stabilile
alkali metal salts has been extended to even more improbable compounds, the
lc.alides and electrides, which exist as complexed alkali metal cations and alkalide or
electride anions. For example, we saw in Chapter 10 that ollc.ali met:lls dissolve in
liquid ammonia (and some amines and ethers) to give solutions of alkoli electrides: 106
(Jl..J8)
However, the situation is somewhat more complica1ed than Eq. 1:!.38 would indicate,
because the electrons Clll react further with the metal to fonn alkalide ions:
(12.39)
Thus, in general, there are allc.ali metal cations. alkalide anions. and electride anions
(and perflaps other minor species) in an equilibrium mixture dictated by various
energetic factors. Note. for example, that because of the eKcellent solwting of the
electride ion by liquid ammonia. the alkalide ions are not favored in these solutii)Os,
and t.h ey are somewh:lt atypical. By using metfiylamine and ether solvents, even
adding solvents of low polarity such as n penl:lne, the equilibria can be shifted and
crystals sometimes grown. I07 The affinity of all:oli metol ions for crown ethers and
cryptands causes cationic complexes to form readily in solution. (See Eq. 1:!.37
above.) 1bis. too will affect the equilibrium, with Eq. 12.38 being shifted to the right
and, therefore, Eq . 12.39 being shifted to the left, by the addition of these ligands. A
rough generalization can be made that excess lignnd will favor the formation of the
electride inasmuch as all of the metal may be complexed as the cation.
Cs +excess 18-crown-6---+
On the other hand. a mole ratio of 2: I,
+ etends to favor the
2Na + 11!-crown-6 ---+ (Na(IS-crown-6))+ + Nn-
(12.U)
Aside from the effects of ligand stoichiometry and the nature of the solvent . there are
also differences in stability of the alkali<le ions. The sodide anion is the most stable.
and the ceside ion the least. Because of differential stabilities of the alkalide ions and
"" IIGlchdor. R. J. : Birdl. T.: 8..,., R. C. lnt"ll CNm. 1916. 2S, 2009-2015. Japn31han. R.;
Wabcc. 0 . W.; uaowsld. J. J. lnorg. C/wm. 1915. 24. II). Knecht. J .; Fisch:r, R.: Ovettd. H.;
Hensel. F. Cbtm. CummU/1. 1978, !IOS-901>. Pl:cr, W. J .: l.:J8owski, J . J , J. ""' Chnn. SIX. 1978.
100. 6260-626 t. For runhcr <lioaouion ol' lhe ox.i<l31iun swld ol' I'Jid ..:c Ch2ptrr ' "
,.. In Eq. 10.:!21hc electron w.u
as (c(NH,),)- 10 cmplwilc lhc solvaaion cll'ccts. Howeer,
jusl as in waiCI' No(H,ot; may be wriltcn as N.;. or I'IIOR simjlly as Na , so al.s o in liqoid
ammoN& lhc solvation may be
by lhc subscript "am," c,;;.. or omitted
"" F an extensive review ol'lhis cherrUtry, sec Dye, J . L. I''Ofl lnurfl. Chtm. t9114, 12, 327-Ut.
F a sllorter, more ru:cnl mric:w, see Dye, J. L. ScJ. Am. 1917, 257{)) , 66-U.
528
12 Coordination C._mislry: Struehwe
differing stability
metal compounds:
Na
of the [M(Iigand)J+ complexes, it is
+ K + 18-crown-6- [K(IS-crown-6))+ + Na-
to fonn mixed
(12 ..42)
As expected , all of these systems are strongly reducing and tend to decompose on
exposure to air and moisture, so very careful work is necessary to study them . In a
few cases. single crystals have been grown and structures determined
crystallographically.108 Thus crystalline [Na(macrocycle))+Na- consists approximately of closest packed, large, complex cations with sod ide anions in the octahedral
holes (Fig. 12.503). The alknlide ions can be found and measured; as expected they are
considerably larger than the alkali metal cations. In fact, the Cs- anion is the largest
known monoatomic ion with a radius of about 310-350 pm. In one salt there is
anion-anion contact giving an effective radius of 319 prn. In addition to the usual
difficulties of assigning an exact radius to an ion. the ceside anion has the added
property that it is not only the largest ion, but also the most polariz;sble.
The structure of [Cs(l8-crown-6)z]+e- has been determined.l09 Decause the
electride anions are extremely poor scatterers compared to the large cesium cation
(and to a lesser extent the C and 0 atoms of the crown ether). the structure has the odd
of complexed metal cations with no corresponding anions (Fig. 12.SOb).
However. the most likely position of the electrons can be inferred from the presence
of cavities of 240-pm radius; presumably the electrons are located in these cavities.
One final example of macrocyclic complexation will be given: From the arguments presented in Chapter 9, the lluoride ion.
should be a strong base and
r.
(o)
(b)
Fig. 12.50 (a) Packing of (NaC222r (large circle$) and Nc- (small solid circles) ions in
(crypWld)SOdium sodide. (b) ORTEP stereo packina diaaram of bis( lkrown-6)cesium
elcctride. The anionic hole ccmers are indicated by the symboi0. (From Tehan. F. J .;
Bomcu, B. L.; Dye, J. L . J . ilm. Ch,m. Soc. 1974, 96, 7203; Dawes, S. B.; Ward. D. L .;
Hucna, R. H.; Dye. J. L J. ilm . Ch,m. Soc. 1986, 108. 3534-3535. Reproduced with
pcnnission.)
II*
For examplc,(K(C222))e-: Ward, D. L.; Huana. R. H.; Dye. J. L ilcta CrytaU11r. Sect. C:
Crysl. Srruc:t. Commun. am. OU, tJ74-t376. (Cs(C222)Jcs- and (Cs(I8C6h]cs-: Huana.
R. H.; Ward, D.L.; Kudlenmeister, M. E.; Dye. J . L. J. ilm. CMm. Sue. 19117. 109. SS61-SS6J.
lOt Dawes,
S. B.; Ward. D. L; Huana. R. H .; Dye. J . L . J. ilm. Chmr. Sue. 1986. 108, 3534-JSJS.
The Chelate Effect
529
nucleophile. Normally. however, it does not show these expected properties because
ils very basicity attracts il to its countercotion so strongly that it is ion-paired in
solution and not free to react. However, addition of. for example, crown-6 to a
solution of potassium fluoride in benzene increases the solubility tenfold and also
increases t.h e nucleophilicity of the fluoride ion. We shall encounter this phenomenon
again in Chapter IS, which covers organometallic chemistry.
Earlier we saw thai chelaling ligands form complexes of greater stability than
those of unidentate ligands. This greater stability was attributed primarily to entropy
effecls but enthalpy effects ore of some importance. Macrocyclic ligands are even
more stable than open-chain chelating ligands. A thermodynamic comparison of
18-crown-6 ccmplexes of No, K+, and &2+ with those of penlaglyme,
CH 3(0CH2CH 2)s0CH3 is shown in Table 12.7. The additional stability is primarily on
enthalpy effect due to preorganizntion of the macrocycle. This is not to say that Jhe
oonformaticn of 18-crown-6 is the same as that found in the complex;
(12.43)
Nevertheless. the energy required to ream1nge the ma.crocyclic lip.ncls for complex
formation is less than the e.nergy required to rearrange pentaglyme into a suitable
conformation. IIOIn addition to their direct structural relationship to biological molecules, macrocycles such as the polyethers may provide clues to the discriminaticn
shown by biological tissues toward various ions. T his selectivity provides the so-
fable 12.7
111onnoclynomic
ccntnbulions to the
mroqclic effect in
No
log K,
18-a-own-6
pentaglyme
log K difference
tJf
Ukrown-6
pentaglyrne
tJf di1ference
-35. 1
- 16.7
- 18.4
-56.0
-43.5
- 36.4
- 19.6
- 19.7
Jkown-6
pallasJyme
llS difference
-33
-71
- 13
- 29
- 84
-33
13
20
comple..s o lll-crOWf>-6
oncl
CH,(OCH:!CH,),OCH.. in
mett-.ol
K..
llS
4.36
1.44
2.92
- 4
6.06
2. 1
3.96
7.04
2.3
4.74
- 23.8
!ttl :!:f
no Crsm, D. l . An.r-. Clwrn. Int. Ed. &gl. 1911, 27, t009-- t020.
"!
Moclilicd rrom Hancock, IL D.; Mal1dt, A . It Commrnt lnarf. Cflrm. JJS&, 6, 237-284. Free
1
and enthalpy dwl&es an: expreued in t1 mol- Entropy cflanaes lltC
ioo 1 mol_
,. .! "-:
530
12 Coonlinarion C.e mistry' StrudVre
called sodium pump necessary for the proper Na+IK+ ionic balance responsible for
electrical gradients and potentials in muscle action. Ill
'The uJtimate in
of metal ions by the ligand is shown by encapsulation
in which the ligand forms a three-dimensional cage about the metal. Tile
resulting case (Fig. 12..51) is called a clathro-chelate or a cryptate. One class of
cryptnte-forming ligands of the type N(CH2CH10CH2CH 20CH 2CH2) 3N has been
called "footbaD ligands" becnuse the polyelhcr bridges between the two nitrogen
atoms resemble the seams of a football. Ugands of thi s type form exceptionally stable
complexes with alkali metals and show high selectivity when the size of the " football"
is adjusted to fit the desired cation. m
Closely related to the football ligands are the so-ealled sepulchrate ligands. One
can be formed by the condensation of formaldehyde and ammonia onto the nitrogen
atoms of tris(ethylenediamine)cobalt(lll). This results in tris(methyleu.:)nmino caps on
opposite faces of t he coordination octahedron. If the synthesis utilizes one of the
(A, A)..enantiomers, the chirality of the complex is retained. Furthermore, the complex may be reduced to the corresponding cobnlt(U) calion and reoxioize<i to cobalt(lll) without loss of chirality. This is patticuJarly unusual in !bat, as we shall see in
the foUowing chnpter, cobalt{ll) complexes are quite labile in contrast to the stability
of cobalt(lll) complexes. Once again the extr:l stability of polydentnte complexes is
demonstrated.
In contrast, BernaJII) has isolated a self-resolving complex whose chirality de
pends only on the conformation of an ac:yl llridge:
c'>II<t
CH,
. . ..c
Single crystals consist of only a single enantiomer, and so in the solid state the
enantiomers do not racemiz.e despite the seeming lack of barriers to rotation of the
rings (see Chapter 13). Presumably crystaJ.packing forces "lock in" the chirality.
Immediately upon solution, the complex racemiz.es, indicating the fragility of the
forces stabilizing it.
'" Rawn, J . D. Bllwml.,ry: Neil Pauencn: &dinal<ln. NC, t989; pp 1024-103-4. Slt)'cr. L
Biochrmislry: Freeman: New Yor1t. 1988: pp
n: lclm. J . M. MJtn". Chrm. Int. 4. &f!. lMS.17. 5-112.
ou Bernal. I .. penonaJ communicaiJOln.
------ -
...
Problems
,.,
[
(b)
531
Fog. 12.51 Cryplate derived from dimethylalyo>time. boron uiftuoride, ond cobalt(lll): (a)
formula; (b) seomctry or cryprore; boron aroms form
on lower left and upper riJI)>t;
coordinate posirions on lhe oelahedton are occupied by nilroten otom1. The heavier Unes
represent eds>c or the polyhedra.. $panned by chelate ri1115. (From Boston. D. R; Rose. N.
J. J. Am. CMm. Soc. 1!168, 90. 6860. Reprocluced with pcrmiuion.j
Problems
of nicl<cl(ll). (Ni0 2(PPb,h). is panmaanetic. The analoa<MJJ complex or

pall.aclioJm(JO is diamqnetic. Pndicl the number or bomcn that will Cltist ror each or
these rormulauons.
12.1 A complex
l2.l Discuss the idenlific:ltion or cis-tram isomers or Compounds
by dipole
b. Di.scuss rhe possibililia o1 idcnrifyinc the cis-trans isomcn of compounds MA1 B. by

dipole momenls.
c. Discuss possibililies ol id.,.,lifying facial-meridional isomcn of MA,B, by dipole
moments.
d. Are rhcre any problm> arisina in octahedrnl comple>les lhD.I make rhis appticarion Jess
certain lhan in squ:tre rl:lnar complexes7
12.3 Thc anions or rhe livc-coordinalc complcxa (CuCI,I'- . (ZnCI,J'- . and

were
isol31e<.las Slllrs or (Co(N H,Ir.l' and (CrtNH,J..f . Expi'.Jin why rhcse counlerions were
chosen.
U.-1 Tho: C'Jiiuns shown in

t2. 1 were isolured us perchlorure. terralluorobonuc. or hexnlluurophosphme s:ohs. OiscUSIO.
12.5 Which diasrereomer. A or B. from Eq. 12.4 is shown inFra . 12. 1S?
12.6 Use rhe clara in Table '12.6 lo calculare equilibrium consranu for the ronnarion
or
(Ni(NH 11J'. and (Ni(enl,f from aqueous Ni1 . Also c:alculare lhc equilibrium constant
ror rhc reaction:
(12.44)
12.7 On the basis ol rhe structures or [Cs(C2221(es- and (Cs(I6C6).J cs-, the cesidc anion
has been sucsrsted as I he
known monooromic ion. Whal orher candidates ror this
disJinctia>III'C possible'! 0o yOU think lhal MY o/1hem will pfOVe IO be latJU thanes?
12.8 Wlty is Jhe producl o1 Eq. 12.42
Jnsre:ld o((NI(IIkrown-6))K- 7
Use a Bom-Haber cycle 10 analyu the etrecr olrhc various f.clon rC$pOnsiblc.
OUI all lhe isomers.
and op&ic:ll, of I he followq: (Co(en),a.J.
[Co(en),(NH.J(:IJ1 . (Co{en)(NH 1h0tJ.
12.' Draw
5J2
12CoordiatiDII Chemistry: Structure
12.10 Draw the mot likely struclure of pcnlaamminecobab(llll-p.thiocyanatupc:ntacyuo

cobalt(l ll)....
12. 11 Which of the two iscmers. Co(Hdma):(SCN)py or Co(Hdma):(NCS)py, would you predict lo be thermodynamically the most stable? Hdma
the monoaruun dimethylglyoximale, HON - C!CH>)C(CH,J- NO'
12. 12 Draw the molecular stn>elure
.1"
or the followina complexes:
a. ci.-dichlorotetracyanochromate(lll)
b.
c. trans-dchlorobis(uimcthylphosphinc)palladium(l l)
d. /ac-tri"'!Uillrinicrocoball(lll)
12. 13 Why does won(ll) hcxacyanoferrJle(lll) spontuneously i$0111Crize to Prussiun blue?
12. 14 Wilh the aid of the cable of liaond obbreviotions aiven in Appendix I find the names of each
of the ligands listed below. Sketch the structure or
liaond and classify it a.s uniclenbidenr..te, tridentate, "tc. Sketch the mode of anxbment of the lipd loa metal ion.
L acac
b. bpy
c. C222
d. chxn
e. dien
r. dmf
11.15
a. dtp
h. edto
1. rod
J. Hedta
Lox
Lpc
m.
n.
o.
p.
q.
r.
phon
pn
PY
tap
tn
tricn
Arlana lhe rollowina six li&ands in ord<er o( incr easina abitity to fcmt stable complexes
and account for your order.
12.16 A recent review of stcric effectS in coordinotion cOmpounds includes che followina
statements concemina stobility:""
Tctnhcclral aeomctry should be more stable than square planar for C .N. 4.
b. Octahcdralaeometry should be more atable thou uiaonal prismatic: ror C .N. - 6.
c. Square antiprismalic seometry should be slialltly more stable than dodecahedral,
which is considenbly more stoble than cubic for C. N. 8.
Discuss these SWemc.JtS in terms of Table 12.1.
" 4
Fronc:zek. F. R.; Schxfcr, W. P. lnor,. crm. 1975, /4, 2066.
n.s Rqhunalhan. S. I . IJt<NB. Nlld. Clwm. 19'75. J7. 2113.

0 . L. .. ComprtlwtUittt CODf'dlnt>IIOtl Owmislry; Wilkinson. C.. Gillan!, R. 0., Me
Clevetty. J. A.. E4s; Perpmon: Oxford, 1987; Vol. I, a..pter 2.
lib Kepcrt.
Problems
533
12.17 The macrocyclic ligand enterobac:tin (F"IG. ICJ.27cl has an cxtraordinlllily hiah affinity for
Fel with a stability constant ollo'l Uhe lnraest known stability constant for Fe' with a
naturally occuning substance) ."'
a. Suggest o sttueturc for I he
compleK that eKplains its high stability.
b. If the concentration of the Fe( lll ..enterobactin complu within the

is
10- 7 molL- , how many liters olbacteria would have to be s..urched to find a single
free
ion?
12.18 In Chapter 6 it was pointed out that X rays nrc dilfrnctcd by electrons. Yel on
528 il
is stoted that the anionic electrons of complcxcd cesium elect ride ..do not show in the
slruclun: determination. Discuss Ihis apparent pamdox . (Hiflt: Why is it hard to locate
hydroaen atoms in on Xray crystaiJoaraphic determination"!)
12.19 Alkali metal und other cationic cryplotcs have been known for a number or years. Mo...,
...,cenlly, anionic cryptatea hove been chArOclerttcd. Sugacst a structu..., for
[0N(CH 2CH 1 NHCH,CH 1NHCH:CH 1))N )-. (Sec Footnote 11 2.)
12.20 Thtte is a complex (C.N. 61 with a chiral mctlll center idustntcd in this chapter that is
not so labeled. Find it and determine iC the iaorncr shown is 6 or 11.
12.21 rtgUrc 12.52 illustrates two forms of the pentanitrocuprate(lt) ion. [CuCNO.lst-. Discuss
aJJ of the types of isomcriml exhibited in these ions."
12.22 T1>e moleaJies shown in
hove chirality? EKplain.
Fte- 1:!. Ia. c appear to be tcft-handed ...
Do these molecule$
12.23 If you lcamed the Cohr>-lnao.._Prdoc rules in org:.nic: chemistry. test your rc:cull by
R.S notation to the molecule shown in Fe. 12..2. Assume that
the CsHs tiB3J>d is a ..single atom .. ol mass 6S U x 13).
l2.Z4 Commercial mayonnai$C. &alod d'""asinss. kidney be:lns. house-plllnl f()O(] . al\ll liquid
dish washing detergents usually contain edtll (see Probkm 1:!.14h) or some derivative of it.
Why? Sec Hart. J. R. J. Cl1t:m. EJuc. 1985. 62 . 15-16.
Fig. 12.52 Two ronns of the
ion. All bond distunces in Angstroms. [From

KlandermAn. K. A. ; HAmilton. W. C.: EemAI. I. /"org. Cht:m. Attu 1971. 2J. 117-129.
ReprO<luc:cd with permission.(
Harris. W. R.; CaiTano, C. J.: Cooper. S . R.; Soften. S . R.: Aydcc(, A. E.; McArdle. J. V.;
Raymond. K. N. J. Am. Cllt:m. Soc. tm, 101. 6097-6104.
110 Klanderman,K. A.; Hamillon, W. C.: Bernal. l. lntxJ. Cllim. Acta tm, 21. 117-129.
117
534
12 Cootdinatio Chemistry: Strvc:lute
12.25 II ;.,
well ami good to say that muc:roc:)'dic polyether.< ''st:lbilize metab. such as
sodium. thai might not otherwise re:.et . .. to form tNU(m:ICrOCyelelt Au salts: but
specifically. in terms or a Born- Haber cycle. wh:IJ pan Juuthe mucrocyelic lig-Jncl play in
the reaction clescribed on paae 526?
a rc.a sonubly c:nreM WOfker. how was it possible for him
12.!6 Ali!luming th.at Piulli was
1u aet "identiclll .. spect111 from solutions of the nitro and nitrilo isomers diacul>Sed on pa&c
5 13?
12.27 R.:ud the section on point groups in Cha4>ter 3 aaain. and identify the symmetry dements
ami operations in 1he molecules and
shown in lhe fisllrcslisted below. Determine the
appropriate point lfOUP fOf cnch molecule
ion.
a. l!.le
b. 12.2a
12.4
d. I!.Su. b
12.7
..
r.
g.
h.
I.
j.
12.10
12. 17
12. 18a. b
12..19a. b
12.20
lt. 12.21a. b
I. 12.22
m. 12.23
n. 12.33
o 12.35b
p. 12.39
q. 12.40
r. 12.41a
12.S3
..
or
the anworlt for u rosearch anicle oc a textbook. the

11.28 Occ:l.sionally. in the preparation
phOIUIIT3phic nqalive a.aken ffOfn the oricinul line dr.lwinc of the ottist is inserted
"ups;cjc-down .. (oc reverse. fronHo-baek) and the rcsultina image is reversed. Does 1his
m;ske any difference? Discuss. Are there any exeeplions to the aener:tl rule? lllustnue
your :lrJUIIICnt with sketches.
12.29
Ihe shapes(i.e . boood ancles. B. and bondlenllhS. J) ofT-shaped (II, >

3nd Yshaped (B, < Bt
B:l molecules (Fie. 12. 1d. e).
e,
&.J
u. Wllal cuuses these molecules to be T,hDped or V-shaped rather thun equilaier:tl?

b. For one or these shapes. J,
Why?
> d1
d!: roc the other. d, < J,
J,. Which is w!Uch?
c. What is 1he point 1roup symmetry of these molecUles?

12 ..30 The cirwlur dichroism spectr.>l dula for the dextrorotatory enontiomer of triS(R.R
Clllion. C+ ,,.,.tCoiR .R-chxnl;,t', if listed in
Tabk 12.5. would appeur as rollows:
.. - ..
20,000
-2.:!8
22.SOO
+0.69
Assi11n lhe correct (4 or M configurJiion to the

l'rublcm
Discuss.
Oo you gel lhe sume answer ns in
12.31 The X-ray CfYSIDI structuro or lhe dexlrorolatory enonliomer of lrisfR.RIranSI.!di

:>minocyelohexanelc:obalt(lll) calion. ( + ),..,. JCoiR,R-chxnl)l"'. may be solved 10 give
Faa. 12.53 as or" of th' two
'"'tnti<mu:rlt snlutions.
a. Is Fig. I!.S3 a 4 or a II enuntiocner?
+"""
b. Does (
tCoCR.R-chxnl,t
o 4 or D II conf\Jur:ttion aboutllle mel:ll? Is your
amwer the same as in Problem 12.30? Explain.
e. Is the isomer (,{or ob'l
d. Are the cllelaJe rinas l'i or A?
12.32 IC either pure A or pure 8 from Equation 12.4 is hcw.:d oi7S 'C in dimethylfon=mide. Ihe
i.omers
un1il1t.!ne is u mix1ure of 40Y. A ancl60"-' B. Why is this not a 56-SO
mixture? Is this a
Problems
535
Flg. 12.53 One of two

pos.'lible enuntiomeric
sohnions to I he X-ray
crystul
or the
dcxJrorotatory en:lntiomer
of trisiR.Rtrmtsl .2di
amlnocyclohexane)
cobuh(llh calion.
( + 1- (COIR.R
See
Problem 12.l l . (MO<lifitd
!tom Sai1o. Y. ltWrlltutic
Mulc-cllldr
SprillGcr-Vertac; Berlin.
1\n'J: p
Reproduced
with pc:nnission. J
for pcntecyanocolxllu ll lh<yanopen12.33 Which u( lhe following is the most likely

[(NH,),Co-cN-cOICNI3 ) or ICNH,!.Co-NC-CoCCNJ,l
Why? 11
12.3-1 Meaallolhionein is round in hurnuns and o1hcr unimaiS. h appc".lrs to remove 1oxic
eldrnium ion from I he kklneys. This protein h:u 7:1 sulrhydryllJroups
func1ion as o
Each mel:ll ion
lhouclu IU be bound to three sulrhydryl
pro1cc1ive chelalins
uoups. Show the probable gcomclry around the cadmium iun when bound to this
chel:llii1Jl "C"nl.
tl.lS
bond lhrous)l lhe oxygen utum. ullhouah thm: :1rc two putential
nitr()!:cn doncr
available us well. Recently ombidentutc bchuvior o( a subs.1iJuJcd
ureo h<ls been demonslrall!d.'lll
form. N.N'bonlkll squure planar
comrl.:xc$ wi1h Ni'" and Cu!' ( l'is. 12.Soial. but N .0-bollllcd cutnfll"' "' with Zn'- 1Fig.
12.5-lbl.
n. Sul!l:e>l u
rc:sliOn
for thi.' beh:tvior.
b. If you did 1101 have 1he X-ruy crysttd struc1urc. whut olhcr cxpc:nmcnl:ll evidence
Obondina und Nbondina in una.? !Hint:
miglu you """ to differenlialc
Compare the analo!;ous problem wilh pNion-bindina silcs. Cb:.rner 9.1
12..34 Twelvc-coordina1ion is ce n:linly r:1re . us

on
liO-S I I,
i5 ano1her
d i..:rctc complex discussed in this chapter wilh C. N. 12. 1houJ;h not NO illcnJificcl. Cnn
you 6ro il?
8-C.: Schaefer. W. P.: Marsh. R. E. lm"JJ. CMm. l r71 . 10. 14<.11-1-1,7.

ao Muslak, P.; Sczepet!..'lki. J. J.; P:lrvez. M. J. Am.
Soc. 1991. 1/J.
119 W:q.
536
12 Coordination Chemistry: Structure
(I)
(b)
Fig. 12.54 O RTEP drawit\JS ol cal dichloro-N.N'-(lpyridylrnethylurea)copper(IIJ: (b)

(From Maslak . P.: Scupanski. J. J.; Pnrvez. M .
J. Am. Ch1m. Stx. 1991. IIJ. 1062-1063. Reproduced whh pennissioo.)
12..37 On pqe $28 1he s1a1emet is made d w "cJYSUIIine (Na(C222))Na- consists approximaJdy ol
paclced. larae. complex c81ions wilh sodide anions in lhe ocaahedral
holes <fia. 12.S0a)." Review lhe discussion ol closes
4 andlabellhe
aloms in Fia. 12.50 as
10 layers A and 8 and indicate 1he oclahedr:>l holes.
12..38 Assume lhal lhe ICQI1lelry
(Fia. 12.4) is lhe resull of the m._.imiza1ion
oC s chiii':ICier loward 1he
bondina phenoxide ions (Benl's rule), allowed (90'
intenc1ions! by the s1erically relaxed cadmium 11om. If zinc is 100 small to accommodate
square planar aeometry and must be pseudotelrnhcdral, how """ il follow 8enl's rule?
Can you ci1e evide.nce to support your case?
12.39 In the disaJssion of (Cd(0Ar):{lh0:1. it was implied 1ha1 h does not hove true Dv.
symmetry. Look closely at Fig. 12.4 and ossian a poln1 aroup symmelry 1o it.
12.40 A chemisl performs 1he roaowina reac1ions:
(I) K:(PICJ.I + !NH,--+ "A"+ 2KO
(2) (PI(NH,t,)(NO.>I: + 2KCI - - + "8"
+ 2NH, + 2 KNO,
She finds 1ha1 bolh A and 8 ore while. diamaanetic,

compounds 1ha1 give
elcment>l analyses for empirical formula PIO,(NH,h. However. A is moSI soluble in
polar solvents. such as elhanol, while 8 is soluble in pelroleum ether (a mix1ure o1
hydrocarbons) and carbon ldrachloride. Draw the structures ol A and B.
12..41 Another chemist reads a report ol lhe experimenl described in Problem 12.40 and
immediately iden1ifies A unci B. Since nickel ia in lhe aame aroup of the periodic table as
platinum, he decides 10 perform the same experirnen1 with nckel(ll) btu is unsuccessful.
He is unable to perform Reac:lion 2 because the startina nwe,r ial, (Ni(NH,),)X,, is not
lisled in any chemical c:ataJocs (he checks for X hUde, niu-ate, etc. ), and none of his
colleaaues lws ever heard ol h . He obtains some Kz NiCI., bu1 when he auempls 10 run
Rcaclion I, lhe Oflly procb:1s he is able 10 isolllle are Ni(NH,),.Oz and KCI. When
triphenylphosphine, Ph,P. is used ;, plaec ol ammonia as one lipnd (ddoride ion is still a
sec:onc! lipndl. compound Cis ilolaced. This compound analyzes for empirical ronnula
NiO:(Ph,P):, and it is l:tftnish. peram:ltnelic. and soluble in cqanic pol:lr solverus.
Regardless o/ lhe reaction conditions or c:oncentr:uions chosen, only Cis round: no oilier
isomers are observed. onw lhe SlniC:IUre of C. WiG il h:lve "dipole rno>rnaJt?
Chapter
13
Reactions, Kinetics,
and Mechanisms
D espite extensive study, inorganic chemistry has yet to achieve the understanding of
reaction mechanisms e!Wyed by organic chemistry. This situation, to which we
alluded previously in Chapter 6, can be attributed to the inherent difficulties involved
in trying to systematize the reactions of more than one hundred elements. Even
attempts to predict from one element to another in the same &fOUP o.re not always
successful. 1be cla.ssic:ll synthetic schemes developed for the hexaamminecoball(lll)
and hexaamminerhodium( Ill) cations illustrate this lo.ck of generality. The preparation
of the cobalt complex involves a combination of ligand displo.cement and redox
chemistry. To the starting material, a s table and common cobalt(ll) salt (such as the
nitrate or chloride), the desired ligand (ammonia) is added in high concentrations to
replace those present; then an oxidizjng aJent (nir or hydrogen peroxide with a
charcoal catalyst) is used to effect the change in oxidation state:
[CoCI.f- -
NH,
[Co(NH3l,f+ -
101
(13. 1)
Simple rhodium(Ill ) slllts, unlike their coblllt counterparts. are stable in water. Thus
the hexanmminerhodium(IIJ) cation can be prepared from reactants that are already in
the + 3 oxidation state:
(13.2)
Because forcing conditions are required in order to remove the last chloro ligand from
rhodium and displace it with NH 3 the reaction is often carried out in a sellled tube at
elevated temperature and pressure.
The hexaammine preparations described above were both devised in the 19th
century. long before reaction mechanisms were investigated. Mechanistic insight
acquired in the latter hlllf of the 20th century has led to the development of more
systematic syntheses for many complexes of cobalt and rhodium . For example. the
hexaammine complexes may be easily prepared by simple substitution of NH 3 for
the CF3SO) (triftuocomethanesulfonato or triftate) ligand in [M(NH,),IOSOzCF3)f+
(M : Co, Rh). a starting material that can easily be obtained from the pentaamminechloro complex.!
' Dixon. N. E.:
G. A.; Lay. P. A. ; Satseson. A. M. IIIDII/. ctm. 1913. 21.146-W.
537
(13.3)
This reaction has fairly general utility because it can be used to synthesize a wide
complexes.
variety of {.M(NH1
Ideally. chemists hope to understand a number of reaction mechanisms well
enough that predictions about a diverse assortment of complexes involving different
metals. ligands, and reaction conditions can be made . A good example of a type
reaction for which this level of understanding has been achieved is substitution in fourcoordinate square planar complexes .
>,Lr+
Substitution
Reactions in
Square Plonor
Complexes
Complexes with d 8 electronic configurations usually are four-coordinate and have

square plaror geometries (see Chapter 12). These include complexes of Pt(ll). I'll( II),
Ni(ll) (also sometimes tetrahedral. of\en octahedral), lr11). RhCI), Co(l), and Au(!II).
Among the d8 ions, Pt(ll) was a particular favorite of early kineticists. Complexes of
PtCII) have been attractive for rate studies because they are stable . relatively easy to
and undergo ligand exchange reactions at rates th:lt are slow enough to
allow easy monitoring. Reaction rate ratios for Pt(ll):Pd(II):Ni(ll) are approximwcly
t: tOS: 107 Funhermone. because isomerization or Jess stable Pt!lll isomers to thermodynamically more stable ones is a slow prooess. scrambling of ligands is not
generally a problem.
There are several pathways by which one ligand may replace another in a square
plunar complex, including nucleophilic substitution, electrophilic substitution , and
oxidative addition followed by reductive elimination. The first two of these are
probably familiar from courses in organic chemistry. Oxidative addition and reductive
elimination reactions will be covered in detail in Chapter IS. All three of these classes
have been effectively illustrated by Cross for reactions of PtMeCI(PMe 2 Ph)z.Z
2_.
PtMe(N1 )(PMe2Ph), + Cr
CIHl
(13.5)
luopllific
(13.6)
The reaction in Eq. 13.S can be thought of as an electrophilic attack by Hg( IIJ on the
platinum-carbon bond. The oxidative addition reaction shows oxidation of Pt(ll) to
Pt(l V) with simultaneous expansion of Ihe coordinotion number of Pt from 4 to 6.
z Cros.. R. J . Owm. S.X. Rn. 1915, /4, tf7-:ul.
Sulutitulion Reodlont In Squor. l'lonor Complexes
539
Elimination of methyl chloride returns the oxidation state to + 2 and the coordination
number to 4 with a net substitution of chloride for methnnide.
Much of what is currently known about substitution reactions of square planar
complexes came from a large number of
studies executed in the 1960s and
1970s.l You should not conclude, however, that details of the mechanisms of these
reactions are of historical interest only. Work in this area cominues unabated as
studies focus on chelation, steric effects. biological reactions, and homogeneous
catalysts. For example. the mech:lnism for the Wacker process (Chapter IS). which
utilizes square planar (PdCIJ1 - as a homogeneous catalyst for the industrial conversion of ethylene to acetaldehyde, is still a subject of investigation.' The overaU
reaction for the process is:
CH1 =CH2
+ !02
NO,
00: CH3CHO
(13.7)
Knowledge of the mechanism may suggest changes in reaction conditions (solvent,

temperature. pressure, etc.) that could improve the effiCiency of the overall process.
As III!Other example, early studies& of the hydrolysis of cis-Pt(NH1}zCI1 are stiU of
interest because of the ability of this complex to inhibit the growth of
tumors (Chapter 19). The biological activity of this compound is believed to involve
coordination of DNA to the PI, and t he details of this interaction arc under intense
investigation.? However. it is gcneraUy agreed th:lt prior to DNA complexation,
chlorogroups ofPt(NH3hC1 1 are reversibly replaced by water. thereby assisting in the
transfer of the drug from the blood to the tumor cells. where the water or chloride
ligands can be displaced by donor groups of DNA."
Ct...,_ /CI
/PI
+H 20
H1N
NH1
J
...,_
[H.O
Cl ]
- 'Pt/
+CI"
/
...,_
H3N
NH3
(13.8)
For the remainder of this section on square planar substitution reactions. we will
confine our auention to those proc.:eding by a nucleophilic p:llh. We tum now to
conl>ideration of the mechanistic details o>f these reactions.
011MIIo. F.: p.,.,.on. R. G. MulwLm IJ' lntlrlllllc"
c<l.: Woley: New Ylltk. 1%7.
Wilkins. R. G. nu Suul.y ,, A'tnrti'u twJ Jlttlwni.mlx t( Hrur1imu o/Trun.Jilion Mt'lul Cmnp/r.tt>.f:
Allyn Wl<l B;x:on: lloslon. lln4.
C. H.: Gray. H. B. Ll11uml Snbllilllti<Hr Proauu:
Benjamin: New Yori<. 196i. Tube. M. L. /mw)!unic H<lfction
Nel5011: Lon<lon. 197!.
Amona rccrnl book.< are : Jdon. R. B.
Mrcllllnbms r{ lmwl(anh: and 0f)lanomwl/ic
Sysmns: Odord UnivcrsiJy: New Yori< . 1991. Wilkiru. 1! . G. 1\iMti<s urrJ Mullllnisms r{ Hroc
timu of Tr111!Sition Mrtul C.-,,rn1. !nd ed .: VCH: New Yori<. 199t. Kal:lkis. D.: Gonion. G.
Mhanimu of lnor11anit: lkat:tions: Wiley: New Vorl<. 191!7. Atwood. J. D.
and
Orllfln..-tallic Rt'OC'Iion Mrchuniswu: Bruok /Cole: Monterey.
1
> ..&.kermart. B.: S6dcrl>crg, B. C.; Hall, S. S. O<KumHntlatlin 14)87, 6, =608. Bllckwll. J. E. ;
..&.kermarl<. B.;
S. 0 . J. Am. Clorm. S>< 1979. lilt . :!-111-2416.
Reishus. J. W.; Manin. D. S . Jr. J. Am. Cltrm. S.x:. 1961. /JJ. 24S7-2462.
'lnqaki. K.; Dijt. F. J.; Lcmpen. E. L . M.; Rccdijlc,
Ctltm. lfC&. 27. 182-J7. Mukundon.
S.. Jr. : Xu. Y.: Zon. G.: Manili, L. G. J. Am. Chlm. S<H'. I, I. llJ.
Bruhn. S. L : Toney. J. H.: Llppord. S. J. Pro11. lm'lr Clu-m. 1990. JS. 417-St6. Reedijk. J.;
A. M. J.; van Oo>lc.JOm, A. T.: v:sn de Pvue. P. Slr..cr. llonding llln'linJ 19118.
67. D-89. Caradonna. J. P.; Lippard, S. J. In Ploti1111m CDINdintJti<Jn Complurs in Cam:rr C'"m<>thrrapy; Hacker. M. P.: Couple. E. B.: Kn>koll', I. H.. Eds.: Mwtinus NijOOif: Boslon. 111114.
so
13 Coordination O.emlatry: Reactia na, Kinetics, and Mechania
The Rate Low
for N ucleophilic
Substitution in o
Square Plana r
Complex
A first step in elucidating a mechanism for n reaction is to determine the rate law
experimentally. The reaction of interest here mny be represented ns
I
T-M-X+YI
L
I
I
T-M-Y+X
(13.9)
in which Y is the entering nucleophilic lignnd, X is the leavi11g ligand, and T is the
ligand trans to X. Kineticists try to simplify their experiments as much as possible,
and one way to do that in this case is to run the reaction under pseudo first-order
conditions.9 Practically, this means that the concentration of Y is made large compared to that of the starting complex so that changes in (Y) will be insignificant during
the course of the reaction ([Y] constant). For reactions in which reverse processes
are insignificant. the observed pseudo first-order rate lnw for square planar substitution is:
k 1lMLzTX] +
rate=
(13.10)
This expression may be rearranaed to give:
rate = (k 1 +
(13.11)
and
(13.12)
From Eq. 13.12 we can see that by repeating the reaction at various concentrations of
Y, we can obtain both k 1 and kz because n plot
against [Y] will give a straight
line with k 1 as the intercept and kz as the slope (Fig. 13.1).
What does the rate law tell us about the nature of the reaction? Substitution
reactions in inorgimic chemistry have been divided into four classes based on the
relative importance of bond making and bond breaking in the rate-determining step:
I . Associative, A. TheM-Y bond is fully formed before M-X begins to break.
2. Interchange associative, /0
The M- X bond begins to brenk before the

M-Y bond is fully formed, but bond making is more important than bond
breaking.
3. Dissociative, D. The M- X bond is fully broken before the M-Y bond
begins to form.
4. lntuchange dissociDtlvr, lr The M- Y bond begins to form before the
M-X bond is fully broken, but bond breaking is more important t.han bond
making.
Nonzero values for both k 1 and kz in Eqs. 13. 10-13. 12 indicate that MLzTX is
reacting by two different pathways. The k1 term, first order with respect to both
complex andY, indicates an associative pathwny, A, similar to the SNJ. reaction or
organic chemist.ry. The term arises from the nucleophilic nttac.k of
by Y. As
To loam bow a kinelicisllhinlc.s,- Espcnson, J. H. CMmkd Kilttfia llltd

McGraw-Hill: New Yorlt,
tMI .
li>lrdtonismr,
Substitution ..octl- in Squo,. Plonor Co..ple...
541
Fig. 13.1 Raae constants
(koo.,, s- 11 as a function o(
nuclcophilc c:onc:entraaMlt!
400
(( Y Dror reaction ol
lrons-(PI(Pyh(l:r.J wilh
seN-
"arious nucleophiles in
350
melhanol at 30 OC. (From

Belluco, U.; Caualini, L.;
Basolo, F.; Pearson, R. G.;
Turco, A. J. Am.
Soc. 1965, 117. 241-246.
300
Used with pcnnission.(
2
200
150
100
50
ar-
c,tt,SH
NO-
10
10-llYJ
would be expected for a reaction in which bond making is important, rates of reaction
depend marlcedly upon concenlration of Y. Fl.lrthermore, the rates are significantly
dependenl on the nature of Y.
At first glance I he k 1 term. first order wilh respect to complex and independent of
Y, would suggest a dissociative pathway. Strong evidence, however, supports the
view that this pathway also is associative. It must be recognized that, in general,
solvent (S) molecules will be nucleophiles and will therefore compete with Y for
to form
(sometimes called the solvento complex). Thus the two-term
rate law could be written as:
..
+ k1[ML1TX]{Y]
(13.13)
However, because the solvent is present in large excess, its concentration is

tially constant and therefore lc'[S) = Jc 1 As a result, Eq. 13. 13 simplifies to Eq. 13.10.
The two associative pathways are summarized in the following reaction triangle:
(J3.J4)
542
13COMdiolio Ch...,itlry: lhtoclions, Kinetics, and Mechanisms
As mentioned above, the k 1 term of the rate law shown in Eq. 13. 10 could also
arise from dissociation (D) of X to give a three-coordinate complex which then reacts
withY.
(13.15)
In other words, the form of the rate law does not help one distinguish between an A (or
I,.) and D (or / 4 ) mechanism for the k1 pathway. The ambiguity in the interpretation of
the k1 term has caused much discussion and experimentation. It is found that reactions
take place faster in more nucleophilic solvents, suggesting that solvent attack plays an
important role.
Also, dissociative reactions should be accelerated by the presence of sterically
demanding ligands; just the opposite is observed, in keeping with an A or I,. mechanism.
Further insight into the question of an associative versus a dissociative mechanism can be provided by thermodynamic data such as that shown in Table 13.1 for the
substitution of bromide by iodide or thiourea in
PEt,
R-Pt-Br+X- R-Pt-X+BrJ
I
(13.16)
X =I or SC(NI92; R = 2.4,6-Me3<;_H2
The reaction rate is primarily determined by the enthalpy of activation (tl.H*). which is
usually the case in square planar nucleophilic substitution reactions. Of greater
importance, so far as a dissociative versus an associative mechanism is concerned, are
the entropies and volumes of activation, M* and ll.V*, respectively. Note that the
values are negative for both the k 1 and the k 2 steps. The observed decrease in entropy
is what we would expect for a mechanism in which two particles come together to give
an activated complex. The volume of activation is determined by doing the reaction
under high pressure:
ll.V* = RTin (kzlk 1)
(13.17)
(P 1 - Pz)
An activated complex with a smaUer volume than the reacting species will give rise to
a negative ll.V* and is characteristic of association (see page SS3 for further discus-
Table 13.1
..
Adivation po..-en lor

the ....,clion of trons-
wit!! r ond wit!! SC(Nfit)2

in methonol0
- -=-=-
...
A""Zn ,
sion).IO For all of the above reasons it is believed that square planar nucleophilic
substitution reactions proceed by association rather than by dissociation.
Many experiments have been carried out to gain a clearer understanding of the
details c:l the associative mechanism. There nre two key questions to be answered:
What effect does the nnture of the entering group have on the rate of reaction nnd how
does this effect alter our view of the intimnte mechanism? The same questions have
been asked with regard to the leaving group, the liaand trans to the leaving group, the
ligand cis to the leaving group. nnd the nnture of the central metal itself. In all
observed renctions,the
group occupies tht site vacated by the
group,
and any reasonnble mechanism must nccount for this experimental fact.
The Trans EHact
None of the nbove facton has been studied more exhaustively than the effect of the
ligand trans to the leaving group. By varying the nature of this ligand, it is possible to
cause rale changes of many orders c:l magnitude. Funhermore, the effect can be used
to advantage in designing syntheses.
The presence of large deposits of plntinum ores in Russin led to an intensive study
of the coordination compounds of plntinum early in the development of coordination
chemistry. As a result of these studies by the Russinn schO<JI, the first stereospecific:
displacement reaction (and first exnmple of the trans effect) was discovered. Consider
two means of
diamminedichloroplntinum(ll): (I) displacement of CC ions
from [P!CI4
by NH,; (2) disp.laccment of NH, from [Pt(NH,)J2 by a- ions. It is
found that two different isomers are formed:
r-
.......
-cr
platlnurrt lll (Nol found

in ellis reaction)
(13.18)
ds...ti;smmine<Jichloropbdnurnlll)
(E..ctusivc poclucl)
Sol"""'
"'N"8Qiivc values for AS' and .1 V* do not prove 1ho1 3 roaction i$ associative.
rearpNzation
can lad w u""xpected entropy chanJCS and conlr'ibuiC 10 overall volume chanaes. Howcver.larlc
ncaotive volucs, such as loose in Table ll. l. are aenenly aeceptcd as indicalina 1111 associati""
mechanism. See /f10f710t!ic Higll
Klnf'flc:s ami Mn:hanismJ; van Eldik. R ..
Ed. : Elsevier. Amstmlam. 19116; van Eldik, R. ; ASQtiQ, T .: t..:Noble. W. J. Clr,.m. Rev.
89.
p,.,,.,
tm.
S49-6113.
II Evidence for a
mech::lnilm lw been reponed: Lanu. S. ; Minnill. D. ; Moon:. P.:
S:lchinillis. J. ; Romeo. R.; Tube, M. L llldl(. Cit"' 19114, 21, 4428--1-433. The rw:lion , which
involves slilslitUiion of dm.o in PIR!(dmsob. proc:ccds by tos.s of one dmso tipncl. However.
becaux il is pos.<iblc 1t.1 lhc dmso li8and llw remains c:oordinalcd e11n l'uloctioo in a chclalins
QIXKi1y. il can be clcbolccl. u Ihose "'<lRcn ..:knowlcdac ..tlclhct INs ruc:cion can be called a
""" disoocialiun.
,w :v :
.,.f.
FJg. 13.6 Dependence or

t_ on concentration or
cntcrina aroup (SCI'<) in

H,O aubstitu1ion involvina
a CO{lll) hcmntoporpllyrin
complex. [From A eischcr ,
E. 8.; Jacobs, S.;
Mcstichelli. L . J . Am
.01
.02
,OJ
.04
.05
Ch1m. Soc. 1968, 90,

2.S27-2.S31 . Used with
pcrmission.l
ISCN"IM
T.W.1 3.
Rote .....-fortloe
.....,;, of
(C..(NJ.b!s(H, Olrt w ill!
xNcsaNO)
SO!-
x-
It (M- 1 . - 1)
10-
10-6
2. 1 x 10....
2.3 X 10....
2.0
[Co(NH3),CH20))3+
Basolo. F.; Purson.

R. G. lolrt:htJIIilml of
2nd
/tltlfltltlic
cd.; Wiley: New Yorll,
1967.
Table 13.5
- COflstcmb " " "'

, --..,
with
x-
It ,.- ,
NCS-
5.0
H1PO;
2.6 X
NO)
2.7
)C
lo-s
1.2
)C
10-6
a-
SO!" Basolol
lL G.
o-10
to-7
1.7 X 10-6
of
This expression simplifies to Eq. 13.30 with

kK{LI under pseudo first-order
conditions. Fur1hermore, the form of the rate law does not change if bond making
becomes more important than bond breaking U.,). Since rate laws for D. 14 , and /"
cannot be distinguished with certainty (knowledge of rate and equilibrium constants
for individual reaction steps may provide clarification). it is not surprising that there
have been oonsiderable debate and controversy over the mechanistic details of many
octahedral substitution reactions. Few reactions appear to fit into the limiting D and A
categories; thus most discussion centers around the 14 and 1, mechanisms.
Because of the inertness of Co(IJI) and Cr(lll) complexes, their substitution
reactions were the first amorc those of octahedral complexes to be e xtensively
studied. Most evidence supports the 14 mechanism for substitution in Co(lll)
plexes. First, there is little dependence of reaction rates on the nature of the incoming
ligand. If bond making were of sienilicant impor1ance, the opposite would be expected. Data are presented in Table 13.4 for the anation react.i on of pentaammineaquacoball( OI):
X"- __. (Co(NH3l,Xl"'+
H1 0
/norttlllit: R l'Dt:I ID<ts, 2nd

cd.; Wiley: New
yon,. - j
i.:U
(13..35)
We see only a small variation in rate constants for a variety of anionic X"- ligands. It
is instructive to also consider the reverse reaction of Eq. 13.3S, aquntion of the Co(lll)
comple x . If this is an 14 reaction, M-X bond s trength should correlate with reactio n
rate since most of the activa tion eneray would be associated with bond b reaking.
Table 13.S satisfies our expectation t h:lt the reaction rate depend s o n the kind of
M-X bond being broken . T he e ntering group nnd leaving group data provide convincing e vidence for a dissociative m echanism and this view is fur1her s upported by
s teric arguments. 1l1e reaction in which water replaces Cl - in [Co(NMeH2),Cl)2 +
takes place 22 t imes faster lhM the same reaction for [Co(NH3),CJ)H . ts The greater
s teric requirements of methylamine encourage dissociation of the Cl- ligand. If the
reaction proceeded by an / nor A pathway, the order of rates would be the opposite
because increased steric repulsion of the incoming ligand would be expected to slow
the reaction. Finally, it should be noted thnt the absence of n trans effect (so important
in square planar substitution) for Co(lll) complexes is consistent with n dissociative
mechanism.
There is growing evidence that substitution reactions in Co( Ill) complexes may
11()t be typical of octahedral transition metal complexes. Early studies of substitution
reactions for CrtIll) complexes revealed n rather strong dependence of reaction rate
0. A.; FolUnllll, 8 . M.; 8111eaon. A. M. /nor,. Qrlrrr. 1970. 9, 1790-t79S.
Kinetics of Octahedral Substitution
Table 13.6
V"'- of oclivation far
..,_,t -"-9!
in
(M(NH,),(OH:t)J'
O;jJ
cr
RhJ+
rr
t.V*, cm2 rnor1

+ 1.2 (300 K)
- s.8 <298 K>
-4.1 (308 K)
-3.2 1344 K>
Doc:ommun, Y.;
Me<bach, A. E. In
lnortonic High Prusurr
Chrmistry; van Eldik, R.,
Ed.; Elsevier: Amslmlam,
19l!6.
Reoction Rates
Influenced by Acid
ond Bose
on the nature of rhe entering group,l9 which supported rhe / 0 mechanism. More
recently, high pressure oxygen-17 NMR spectroscopy has come into widespread use
for obraining mechanistic details abool fast reactions and, as a result, many waterstable transition metal complex ions have been investigated. The parameter of interest
lhat is yielded by these experiment.s is volume of activation, AV*, which is a measu re
of the change in compressibility that occurs as the reaction proceeds from the ground
state to the transition state (see page S42). The data in Table 13.6, obtained for solvent
exchange with (MINH,),(H,O))'+ complexes. show a positive AVt for CQ}+ but
negative values for
Rh)+, and lr' +, suggesting an 14 mechanism for lhe cobalt
ion but 10 for chromium, rhodium, and iridium ions.lO Data for water exchanee
reactions of first-row hexaaqua tripositive ions are shown in Table 13 .7 . We see a
general increase in volumes of activation as we move across the periodic table from
Ti(III} to Fe(UI). In fact the value for Ti(lll) approaches that predicted for an A
mechanism.l l The trend may be viewed as a gradual change from strongly associative
to moderately associative. SimiiM NMR studies of solvent exchange reactions also
have been canied out for divalent transition metal ions,
In these
experiments, volumes of activation indicate a change from /0 to 14 across the first row;
i.e., the dissociative mechanism is more important for Ni(II) than for Fe(ll).ll Since
volumes of activation also include volume changes in solvents and reactants. interpretation is not always straightforward, and some believe that the power of the
method has been overstated. For example, L.anafordll and Swnddlez have presented
opposing views on this matter. Undoubtedly, the 1. pathway is more common for
octahedral substitution than once thought.
cr,
Substitution reactions taking place in water solution can often be accelerated by lhe
presence of an acid or base. If the coordinated leaving group (X) has lone pairs which
can interact with H+ or metal ions such as Ag+ or Hi+, the M-X bond may
be weakened and loss of X facilitated.ZJ This effect is seen in the nquati.on of
(Cr(H20)5 Ff+:
(Cr(H 20l5 FJ 2+
T..t.Je 13.7
(Cr(H1
Volumes of aclnralion far

water
in
hooquo campi of
transifton metal ions of 1M
first row
M
t.V*, em mol- 1
Ttl+
v.)+
cr
3
Fe
- 12. 1
- 8.9
-9.6
-5.4
553
+ W :;::::: [Cr(H 20 >, -F-H)>+
0)1'"-F-H)3 +
+ H20
---+
(13.36)
+ HF
(13.37)
Available lone pairs of the bound fluorine group are auracted to rhe hydrogen ion.
leading to the formation of a weak acid. The rate constant for the ovemU reaction is
6.2 x w-o s - in neutral solution, but 1.4 x 10- 6 s - in acid solution. When
19
Espcnson, J. H. lnorg. Owm. 1969, 8, 15S4- IS56.
.., Ooco<nmun. Y.: Merbach, A. E. In lnorrtJnlc Hith Prtuurt Chtmis1ry; Vlln Elclik. R.. Ed.;
Elsevier: Amstcnl:lm, 1986. """ Eldik. R.; Asano, T .; Lc Nobk. W. J. Chrm. Rt11. 1919, 89,
Hual. A. 0.; Helm, L;

Me<bach. A. E.
Clttm. tm, 26, 176}.-1768.
Xu, F.C.; Krouse, H.
ts-ddle. T. W. lfiO'I.
R.;1
IC\rm. IMS, U, 267-270.

Swaddle, T. W.; Me<bacb, f
E. II)Otf. Cllnn. 1911,
20,
......_:J
549-688.
Hllgi, A. 0 .: Helm. L.: Mcrl>ach. A. E. /ltt>fJI, Chtm. 1987. 20. 176}-1768.
"'Lincoln, S. F. : HllUnslow, A. M.; Bolta. A. N. lnortt. Clttm. 1986, lS. 1038-1041.
n
C. H . /,tHg. Chtm. 1m. 18. 3283-3289.
z Swaddle. T . W. /no(%. Clum. 1, ., /9, 3203-l20.S.
u Han! lipnds such as F - arc most etrcaivcly removed by Nird metal ions liiCh as Be>+ and At+,
but sol\ liplds such as cr, Br- , and 1- arc beucr
by soil metal ions sud\ as At. and
>t
Ha.
ammonia. which possesses no free lone pairs when it is bound to a metal, is the leaving
group, no acoeleration is obscrvcd.26
Hydroxide ion also may have an appreciable effect on the rate of hydrolysis of
octahedral complexes. The rate constant fo r hydrolysis of [Co(NH3) 5CI)2 + in basic
solution is a million times that found for acidic solutions. Furthermore, the reaction is
found to be second order and dependent on the hydroxide ion concentration:
rate = k[Co<NH,),CI2+)[ow )
(13.38)
Although an associative mechanism is consistent with these results, the prevailing
opinion is that the reaction takes place via proton abstraction:
[Co(NH,>,CI]l+
+ OH -
[Co(NH 3MNH 1 )CI)+
[Co(NH3MNH JCi]+ - - + [Co(NH,).{NHz)]2+

[Co(NH3).(NHz)]2+ + H 2 0
H 20
+ CI-
...!!!... (Co(NH,),(OH)]Z+
(13.39)
(13AO)
(13.-41)
According to this viewpoint, the hydroxide ion rapidly sets up an equilibrium with the
amidocobalt complex. The rate-determining step is the dissociation of this complex
(Eq . 13.40), but since its ooncentration depends on the hydroxide ion concentration through equilibrium, the reaction rate is proportional to the hydroxide ion
concentration.
This mechanism, assigned the symbolism SNica for a first-crder reaction involving the colliugate base of the complex. is supported by a number of observations. It
rationalizes the fact that the hydroxide ion is unique in its millionfold increase in rate
over acid hydrolysis; other anions which are incapable of abstrncting protons from the
complex. but which would otherwise be expected to be good nuclcophiles. do not
show this increase. Furthermore, the SN i ca mechanism can apply only to complexes
in which one or more ligands have ionizable hydrogen atoms. Thus oomplexes such as
[Co< py)4 CI2 )+ and [Co(CN),CI)'- would not be expected to exhibit typical base
hydrolysis and indeed they do not. In these cases, the hydrolysis proceeds slowly and
without dependence o n hydroxide ion.
If the hydroxide ion accelerates reuctions by proton abstraction rather 1han by
direct attack, it might be supposed that it would be possible to trap the five-coonlin.,te
intermed iate by addition of large amou nts of anion other than hytlroxide . One: system
for which this is possible is the base hydrolysis of [Co(NH 2 R),X )! IX
OSO:CF)l
with N) as 1he trapping agent:l7
(13.42)
[Co(NHzR).(NHR)Xr -
(Co(NHzR}.(NHR))l +
x-
(13.43)
._./H,o
(13..$4)
1ft Wilkins.
R. G. Kinriks and MlrDrbms of R'llclions of TtttMitintt .\t.,fll
t99t.
n Curtis. N. J.; Lawrance. G. A.; Lay, P. A.: SlrJqon, A. M.
2nd ed.:
VCH: New Ycotc.
Chrm. 1916.25. 484-488.
Kletics of Odohetlrol Subtlitutio
555
When this reaction wns carried out in 0. 10 M hydroxide and 1.0 M azide, both the
hydroxo (90.3"/.) and azido (9. 7"/.) complexes were fonned. Keep in mind that without
base, azide substitution would not be observed within the experimentnl time period.
Furthennore, the rate of hydrolysis is not much different when azide is replaced with
perchlorate or acetate. It becomes clear that these anions are spectators of the fivecoordinate activated complex and are not involved in the loss of
The preceding discussion of substitution mechanisms barely scratches the surface
of a field that has occupied the attention of many or the wor1d's best coordination
chemists. II is an area which seems to have an infinity of problems ns well as methods
of attack. It is unfortunate that it is not possible here to present a more comprehensive
theory or substitution mechanisms. The discussion presented em on the side or
omission or fine points and controversial interpretations . For every eXperiment designed to confinn a mechanism, an alternative explanation can usually be found. As
one noted researcher once said: "[The members of the other school of thought) are
extremely ingenious at coming up with alternative explanations for all of the conclusive experiments that we seem to do. ''21 This should serve to remind us of the
truism that it is not poSSible to prove that a particular mechanism is the correct one; it
is only possible sometimes to prove !hal a n alternative mechanism is not correct. To
this might be added a corollasy: Often it is extremely difficult to prove that the
alternative is impossible.
x-.
Racemization and
Isomerization
Another set of reactions that has received conside.rable attention is that in which
optically active complexes, e.specially tris(chelale) compounds racemize:
(13.45)
There <Ire seve roll mechanisms that are possible for such an inversion. some of which
can be eliminated by appropriate experiments. FOI" example. one mechanism would
involve complete dissociation of one chelating ligand with formation of a square planar
or a trans diaqua complex as a first step:
+2 H,O
(J l.46)
I
oH
::a Ptancn. R. G. In Mhunistn.r of lntNgUIIic: RI'OCJitJM; KklnbctJ. J . Ed.; Advancca in Olcmislly

9: American Chemical Society:
oc. t96S: P 2.5.
556
13 c-rdlnolion Chllftlislry: RIIOCtions, Kinetic., and Mechonioms
lbe dissymmetry would thus be lost, and when the chelate ring reforms, it would have
a SO-SO chance of producing either the A or /1. isomer (Chapter 12). Since the ratedetermining step in this mechanism is the dissociation of the ligand, the rate of
racemization (k,) would have to equal the rate of dissociation (k4 ). For example,
tris(phenanthroline)nickel(ll) racemizes at the same rate (le, .. I.S x to- s - 1) as it
dissociates (le4 = 1.6 x 10- 4 s- 1) , which implies dissociation is part of the racemization mechanism. If racemizalion takes place faster than dissociation (as it does. e .g.,
for tris(phenanthrolinc)iron(ll): le, .. 6.7 x to- s- 1 and le4 - 0.70 x to- s- 1}.this
mechanism can be eliminated.
For cases that involve dissociation, it is probable that only one end of the chelate
detaches with formation of a live-coordinate complex. This complex could have either
trigonal bipyramidal or square pyramidal geometry and either of these could undergo
Berry pseudaotation (sec Chapter 6) with
of ligand sites. Reatt.ochment of
the dangling end of the bidentate lipnd to reform the chelate ring would give a racemic
mixture of A and /1. isomers.
For many complexes, le, > k"' which means that racemization occurs without
bond rupture; for these, an intramolecular pathway must be operative. Four symmetry
allowed intramolecular pathways have been identified (Fig. 13.7).29 The "push
through" (six coplanar ligands) and the "crossover" (four coplanar ligands) mechanisms both require large rnetaHigand bond stretches to relieve steric hindrance and
areencrgeticallyunfavorable. '1'wist'' mechanismsrcquitemorcmodestbondstrctches
and are believed to account for the racemizalion . The earliest twist mechanism,
proposed by Rly and Dutt,lO is known ns the rhombic twist . Some yc:us later, Bailar
suggested a trigonal twist mechnnism.ll lbe RAy- Dun twist involves rotating a
trigonal face that is not associated with a threefold axis of the complex through a C2
transition state into its mirror image. Thc Bailar twist can be seen as twisting a
complex about a threefold axis through a trigonal prismatic transition slate into its
mirror image. It is a commentary on the experimental difficulties encountered that so
many years have passed with little lirm experimental evidence in support of one or the
other of the mechanisms. It appears that rigid chelates and those with small bite angles
favor a trigonal twist.ll Small bite angles are known to stabilize trigonal prismatic
geometries (Chapter 12) and thus might be expected to reduce energy barriers to such
a twist. Calculations suggest that the trigonal twist is favored when the bite b, defined
as the distance between donor atoms in the same chelate ligand. is substantially
smaller than / , the distance between donor atoms on neighboring chelate ligands (see
Fig. 13.7).ll On the other hand. for a rhombic twist to be favored. b must be much
greater than /. It would appear that both mechanisms are rather common because
many complexes belong to each geometrical class. In cases where b and I are not
significantly different, both twist mechanisms may operate simultaneously. Intramolecular isomerization of cis and trans octahedral complexes, M(CQ)4 L L' , is also
well established for some complexes and probably proceeds through a trigonal twist
mechnnism.l4
,.. Roclaer. A.; Johnoon. B. F. G. tnorr. Clwm. tM. 27. J06t-l062.

RJy. P. C.: Ouu. N. K. I . lnditln Cirm. Soc. t90. 20. St.
ll Bailar. J. C.. Jr. I . IIUNJ. Nucl. Otnrl. 1958, I, t6S-t1.S.
Kepett. D. L. Pt()f. tnorr.
1m. 1J,
RociKer. A.: loi!Non. B. F. G. lnort.
tna. 27, 106t-l062.
,..
0. J.: Gny. R. L.lnor,. Chrm. ,_,..., 2J, 2993-2996.
Mecha ni11m1 of lt..laa lteoctiano
557
Iii
T . Cl>
Fig. 13.7 Four intl'llmOiecular mechaniamS for racemiZAtion of a uis(chcla!e) a<:tahecln l

complex (R reac1an1 ; T
transition SIDle; P product). Only the Bailar and RAy-Dun
tWisto are enerJCiically acceptable. (Modified from Rodier. A.; Johnaon. B. F. G. l nOI'g.
Ch tm. 1988. 27. 3061- 3062. Used with permission.)
Mechanisms of
Redox Reactions35
It might be assumed that there would be lillie to study in the mechanism of electron
would simply bump into
transfer-that the reducing agent and the oxidizing
each other and electron lransfer would take plnce. Reactions in solution are complicated, however , by the fact that the oxidized and reduced species are often metal ions
surrounded by shields of ligands and solvating molecules. Electron transfer reactions
Taube, H. &c11011 TrtiiU/tr Rtodiolll Q{C<>mpltx ION In Solution; Academic:: New Ycrlt.. 1970;
Chap(..- 2. Haim A. Ace. Clwm. Rrs. l!riS. 8. 264-l72. Ptnnin&ton, D. E. In CD<>rdilaion
Oormtstry; Mar1dl. A. E., Ed.; ACS Monosnph 174; American Chemical SoQety:
DC. 19'111; Vol. 2. pp 476-S90. Ta<be. H. Scittnct 1914,126, 1028-1036 (Profes3orTa.Jbe's Nobd
Prize
"All
of Henry Tllube." Prot. lnort. C,...,. IJIJ, JO. Rudolph A.
Man:us Com..-.oneivc Issue, J. Plrp. Cfwm. 1916, !10, 3453-3862..
558
13 Coordinatio n Chemistry: lleodi-, kinetics, and Mechanism
involving transition metal complexes have been divided into two broad mechanistic
classes called outer sphere and inner Sphere. In this section we will compare these
mechanisms and examine factors which influence reaction rates for each.
Outer Sphere
Mechanisms
In this type of reaction bonds are neither made nor broken. Consider the reaction:
(13.47)
Such a reaction may be considered to approximate a simple collision model. The rate
of the reaction is faster than cyanide exchange for either reactant so we consider the
process to consist of electron transfer from one stable complex to another with no
breaking of Fe-CN or Mo- CN bonds.
An outer sphere e lectron transfer may be represented as follows:
0 + R--+ [0-Rl
(]3.48)
[0-R] --+ [0-RJ
(13.49)
[0-R] ____. [0--R+]
(13.50)
ro- -RJ -
o- + R
(JJ.SJ)
First the oxidant (0) and reductant (R) come together to form a precursor complex.
Activntion of the precursor- complex, which includes reorpnization of solvent molecules and changes in metal-ligand bond lengths, must occur before electron transfer
can take place. The final step is the dissociatioo of the ion pair into product ions.
A specific example further clarifies the activation and electron transfer steps. 1bc
exchange reaction between solvated Fe(lll) and Fe(IJ} has been studied with radioactive isotopes (Fe) of iron.l4
[Fe(H20 ),J+
+ [Fe 0(H20)11f + --+
+ [Fe(H 20 )6]'+
(13.52)
The energy of activation, AG'. for this reaction is33 kJ mol- 1 One might ask why it is
not zero since the reactants and products are the same. In order for electron transfer
as
to occur. the energies of the pnrticipating electronic orbitals must be the
required by the Franck-Condon principle.n In this reaction an electron is transferred
from a 1!, orbital of Fe(II) to a '2N orbital of Fe( III). The bond lengths in
and Fe 3
complexes are unequal (sec Table 4.4), which tells us that the energies of the
Is
are not equivalent. If the electron transfer could take place without an in pot of energy.
3
we would obtain as products the Fe(II) complex with bond lengths typical of Fe and
the Fe( Ill ) complex with bond lengths typic.a l of FeH; both cou ld then relax with the
release or energy. This would clearly violate the first law of thermodynamics. In fact,
there must be an input of energy in order for electron transfer to take place. The actual
process occurs with shortening of the bonds in the Fe{ II) complex and lengthening of
the bonds in the Fe(lll) complex until the p811icipating orbitals are of the same energy
(Fig. 13.8). Vibrational stretching and compression along the metal-ligand bonds
allow the required configuration to be achieved.
1bc energy of activation may be expressed as the sum of three term.s :
10 Sykes,
l>
A. G. Kinltla of ln<Ngonk
Porpmote Oxl'onl. t966:
L.cwis. N. A. J .
Educ. 1'*'. $1, 4'78-4).
2.
Meeh...,isms of l..loa lleodioM
I
/1 "
ott,
3+
HO
H,o, OH
1 ;oH, ". /
Fe
/ I '
H10
Ott 1 OH,
559
2+
OH
'
....
H10
OH,
Ott 1
f1g. 1l.8 Extension and eompn:ssion o r the

bond$ in [Fc(H 10l.f+ and
[Fe<H:OJ.f+. respectively, to fonn an aetivatc.J complex in which all mcuJ..tipnd distances
are identical. a prercquisile f e lectron
between the two complexes. [From Lewis.
N. A. J. Chrm. EJuc. t!ISO. S1, 478-183. Uaed with pcnnission.J
in which AG: is the energy required to bring the oxidant and reductant into a
configw-ation in which they are separated by the required distance (for
reuctants this includes work to overcome coulombic repulsion),
is the energy
required for booo compression :md stretching to achieve orbitals of equal enerJy. and
is the e nergy needed for solvent
outside of the first coordination
sphere.
Potential energy diagr.uns fun her clarify the connection between molecular motion and electron transfer . The potential energy of all reoctnnt and assOOllted solvent
nuclei before e.l ectron transfer can be opproximnted os a harmonic potential well
(F.g. 13.9a. RJ. The potential energy of :Ill product and solvent nuclei after electron
can be described similarly (fig. 13.9a. Pl. The reac1ants and products of Eq.
13.52 have the same energy, as shown in Fig. 13.9:1 . At the
of potential
orbilal encrgie:s is met . For electron
energy surfaces. I. the requirement uf
tmnsfer to occur at I. however, coupling of vibrational and electronic motion must
take: place. The extent of thi.s interaction is relate.J to !l shown in the figure. If the
coupling interaction is stro11g, which is the condition when bond distortions are smaD.
electron transfer is favorable. If the interaction is very weak, associated with large
bood distortions. ll.G: wiU be large and the reaction will be slow. These considerations
are equally applicable to heteronuclear reactions as depicted in Fig. 13.9b.
The impor1anee of bon.J distonion magnitudes is revealed in the self-exchange
reaction of hexaamminecobalt complexes:
[Co(NH 3)Jl+
[CotNH 3)J2
+ [CoCNH 3)6JJ+ (13.54)
The second-<Jrder
consl:lnt for this slow reaction is 10- c. M- 1 s- t.n The Co-N
bontl length in Co{ Ill) is 1.936( IS) Awhile in Co( II) it is 2. 114(9) A, a difference of
0.178 A.'1'1 Considerable elongation of the Co(lll>-N bond and compression of the
"' H:unmershi. A. ; GcsdowitL 0 .: T<dlc. H. lftiH'I.
l,_..,JJ, 979-98Z.
"'Kime N. E.; tben. J. A. MID C,.tcJiorr..
8 : SttUC'I. Sd. lf69, 2J, t68.
560
13 Coordlnotion Chemistry: Reactions, Kinntics, ond Mechanisms
..
li
i2.
:0
:ii
(OJ
Fig. 13.9 (a) Potential enetJY diagram for a bomonudear dcctron trantter reaction such as
(fe(H10).r + (Fe(H,O),J)+ ---+ (Fc(HtO)J' + [Fe(HtON.f
or
(b) Potential energy dia&ram ror a heteronudear elearon trantlrr reaction. Each dia.,.am represrnts a cross section
the
total pOtential cneray
reactants (R) and products (P) in coqur:uionaJ apace. Electron transfer may occur at I, the
inlerslion
U.e two pOtentilll <IOCI'IY surfaces. where the encfliea
the pe.rtic:ipll.in& Ottitals arc equal.
or
or
or
Co(II)-N bond is necessary before electron transfer cnn occur. In contrast , the selfexchange rate constant for the
couple is 8.2 x rol M'"" 1
s -t and the Ru- N bond length difference is 0.04(6) A. 40 This much faster rate for the
ruthenium exchange is consistent with a smnll bond length adjustment prior to electron transfer . The cobalt and ruthenium systems ore not entirely nnalogous, however,
since cobalt goes from a low spin tf' complex to n high spin cf1 complex while
ruthenium remains low spin in both the oxidized and reduced forms. It has been
argued that the cobalt reaction is anomalously slow because it is spin forbidden;
however, recent work does not support this hypothesis.
It should be noted thai not nil self-exchange rcnctio.n s between Co(!II) and Co(ll)
are slow. The nature of the bound ligand has a significant inftuence on the reaction
rate. In particular, ligands with rr systems provide easy passage of electrons. For
[Co(phen)3)3+/[CO(phen) 3)1 + exchange. for example. k is 40 M'"" 1 s'"" 1, many orders d
magnitude faster than for the cobalt nmmine system.l
Marcus has derived a relationship from first principles that ennbles one to calculate rate constants for outer sphere renctions:o
(ll.SS)
To illustrate the application of this equntion and the definitions of nil of its terms, we
will cnlculate the rate constant, k11, for the renction of Eq. 13.47 (called a cross
40 Stynes.
H. C.; tbers, J. A. fnorr.
Larsson. S.; SIAhl, K.; Zc:mcr. M. C.
1971 , 10, 2304-2J08.
tnorr. 011m. lf86. ZJ, l03J-3037.
btorr. Olt!m. IHI, 7, $14-SIII.

> Marcus, R. A. Annu. R,.,. Phys. Chmt. 1964, U, I.SS.196. NeWlOn, T. W. J. Cllnn. t:Juc. IJ68.4.S,
., Farina, R: W'dlcin. R. G.
S71-S7S.
Mechanisms of lledox Reactions
561
reaction as compared to a
reaction). For this reaction. /.: 11 is the r.lle
constant for the self-exchange process involving the
complexes:
[Fe(CNIJ'-
+ [Fe*ICNI"Jl1.:11
---+
[Fe(CN)"Jl -
(13.56)
= 7.4 x 102 M- 1 s- 1
1.:22 is the rate constant for the similar reaction involving the octacynnomolybdenum
complexes:
[Mo<CNII<l,_
---+
(13.57)
kr. =- 3 x 1()-1 M- 1 s- 1
K 1! is the equilibrium conSianl for the overall reaction (Eq . 13.47):
+ [Mo(CN}s,f-
[Fe(CN),]>-
+ [Mo(CN>.J"-
(13.58)
and Jog J; 2
(log K 12 f/4 IOI!(k11kzJZ 1 ) . This last term coouuns Z, which is the
coUision frequency of two unch:lrged p:!rticles in solution and is taken as IO " M- 1
s- 1 The factorJ; 2 has been described as acOCTeclion for the difference in free energies
ofthe two reactants and is often close to unity lin this case it is 0.8.5).._ When all of the
appropriate values nre substituted into Eq. 13.S.5, k 11 is calculated to be 4 x 10' M- 1
s- 1 which compares quite well with the experiment:ll value a 3.0 x to M- 1 s- 1. 4$
Table 13.8 summarizes results for a number of other outer sphere cross reactions.
Confidence in the Marcus equa1ion is high enough that. if it leads to a calculated rate
constant that is in strong disagreement with an experimental value, a mechanism other
than outer sphere should be considered.
The Marcus equation (I 3.SS) connects thermodynamics and kinetics. as shown by
the dependence of 1< 12 on K11: As K11 increases, the reaction rate increases. Thus
outer sphere reactions which are thermodynnmically more favorable tend to proceed
faster than those which arc less favorable. These observations may be surprising to
you since most elementary treatments of reactioo dynamics keep thermodynamics
(how far) and kinetics (how fast) separate. Here we see that how fast a reaction occurs
can depend to some degree on how far it goes , or the driving force, 4G. The simplified
Marcus equation we have presented here, however, breaks down when K 12 becomes
large. The complete theory reveals that rate increases rapidly with increasing spontaneity, reaching a maximum when the change in free energy is equal to the sum of
reorganization energies, and then decreases ns the driving force increases further.
Excited Stote Outer
Sphere Electron
Tronsfer Reoctions
The redox properties of a

metal complex may change dramatically if it
has nbsoroed energy and exists in an excited slate. One of the most famous and
widely studied complexes in this area is triS(2,2'-bipyridine)rulhcnium(ll) cation.
., Pmni'111on. D. E. Ia Cnnrd'11101/Dn crtnistry: Mutttll. A. E.. Ed.: ACS MClnCllf'liPIII74; Ameriaon

Cbcnical Socicly: Washqlon. DC. 1978: Vol. 2. Olapter } .
"'Campion. R. J.: Purdie. N.: Sutin. N. /n<HJI. CMm. 1964. J. 1091- 1094. Chou. M.; O.:Uiz. C.;
Sulin. N . J . Am. C/Km.
m7. 99. $61S-$62J. Su1in. N.: Crewz_ C. J. Chrm. EJ. 1983, 6().
809-814.
562
13 Coordination Chmistry:
ICintics, and M.chanitmt
ToW. 13.8
CoiMclt.d and obs.rvod

cOftltants lor outer
apMre CI'OU reoctions
log
K,,
Fe;; +
+
Fe;;
4.4()
3.39
S.42
1.0 1
0.2S
5. 19
16.90
1.53
3.90
Ru(NH,W +
11.23
Ru(NH,W +
Ru(NH3).sPy2+ +
Ru(NH3W +
Ru(NH3),py2+ +
+ Co<cnW
V!; + Ru(NH3 )!+
v;;
v!_; +
+
Mo{CNJ:- + 11Cir
Mo<CN):- + Mn04"
Mo<a-n:- + HMn04
.Fe(CNJ:- + lrOi
Fe(CN(- + Mo(CN)r
Fe(CNl:- +
MnO;
9.40
2.t8
-4.07
8.48
4.08
2.00
3.40
..""_, .-,
1.4 X
l.lx
l .S X
2.0 X
5.8 X
1.3 X
10'
108
10'
103
10-4
to'
1.8x 10'
1.4 X lo'
2.7 x 104
3".4 X 10'
8.4 X ut
1.9 X
2.7 X Jo'
1.9 X 107
3.8 X
3.0 X
1.7 X to'
lru.-
(M-1 1-1)
4
4
I
I
7
107
X
X 10'
X 10-4
I x lo'
2 X
5 X
6x 106
2x 106
4 X Jo'
8 X Jo'
6
2
JO'
X 107
IX
4 X
6x Ia'
M;ucu, R. A.: SUiin. N. Bilrim. Biophp. Aero ttl$. 81/, 26S.
[Ru(bpy) 3)2+ .44 When th.is cation absorbs Jijht at452 nm.the excited state species that
initially forms. [Ru(bpyhJ2 +. relaxes to a relatively loog-lived one. [Ru(bpy)3) 2 .c
The electronic transition involved in the absorption is an example of a rnetnl-to-ligand
charge transfer in which a d electron of ruthenium is promoted to a .,. antibonding
orbital of one of the bipyridine ligands. Thus the excited state complex,
[Rull(bpyJ,J 2 +, may be formulated as [Rulll(bpy)z(bpy- ))2+. The availability of an
electron in a ligand antibonding orbital makes this excited state calion a much better
rc<.lucing agent than the ground state cation. FUrthermore, the "hole" cren1ed at the
ruthenium center enhances its electron-seeking power and ns a result, the exciteJ
cation
also a much better oxidizing agent than it was in its ground state. A
comparison of the redox properties of the ground state with those of the excited state
is shown in Fig. 13. 10. Here we see that [Ru(bpy)3) 2+ is a better oxidizing agent than
[Ru(bpyl:J) 2+ by 2.12 volts (+0.84 V + 1.28V) and a beller reducing agent by 2. 12
volts ( +0.86 V + 1.26 V). These are large voltages from which one can easily see the
potential for a wide range of redox chemistry.
Whether a complex in an excited state cnn manifest its enhanced redox properties
will <.lepend on whether it can undergo electron transfer faster than it undergoes
something else, such as relaxation to the ground state (luminescence). The emission
lifetime of [Ru(bpy),)2 + in aqueous solution at 25 c is 0.6 p.s and it increases
... Juris. A.: Baloo, V. ; Bati&ekni. F.; Carnp1811a. S.: Bel- . P.: von Zdcw.ity, A. Coord. Clwm.
R.-. 1911. M . IS-m.
T. J. l'ruf(. lltMf(. Qwm. 1913. JO,
Wou R. J. J .
Edoc. 19&3, 60.834-842. Kwal, C. J . 0.1m.
t9&J. 60, 882-887.
41 Earlier we U5Cd M to indicate 1 r.adioactivc isoiOpC. Here we use M 10 indic..ac an exciled stale.
Mechanisms of Redox Reactions
563
Radiobonle#
decay
Ru(bpyl!'
'
Rutbpylr
!elf v
. , ... v
Rutbpyl;
fig. 13.10 Absorp1ion or blue tig)J1 by [Ru(bpylJr gives (Ru(bpyt,f which retoxes 1o
[Ru(bpy),]H wilhout ligl11 emission. [Ru(bpyhf moy emil onngered lighl (luminesce)
undergo oxidalion or reduclion. Slandard reduction p01emials associated wilh individual
processes are shown in lhe diagram. (Modified from Juris. A.: Balzani. V.: Borigelleui. F.;
Compagna, S.: Belser. P.: von Zelcwslty. A. Coord. Cl11m. R1v. t9&1. 84.1!$-271. Used with
pennission.]
substantially at low temperatures. Ths can be compared with the rates for electron
transfer by self-exchange.:
[Ru(bpy)3f
+ (Ru(bpy)3) 3 +
+ [Rulbpy)J] 3 +
--
+ [Ru(bpylJ+ -
[Rulbpy)3)!+
+ [Ru*lbpyl3)
(13.59)
(13.60)
for which rate constams have been estimat.:d to be t()t< M- 1 s- . II is quite clear that
may exist in solution long enough to participate in elec1ron transfer
reactions.
Interest in [Ru(bpyt,f skyrocketed after Crcutz and Smin suggeste<lthm it had
pos:"bili1ic:s for the phoiochcmic:.l cleavage of wat.:r:
H:Ofll
...=... H:lf!l + 40:1g)

= 231! U mol- 1
(13.61)
.l(l11
The su&geslion led to the speculation that solar energy could be used to make
hydrogen gas which could then be used as fuel. At pH 7 and lOS Pa. potentials for 1he
reduction and oxidation of water are as follows:
2e- +
+ H:
+ 10: + 2e-
20HH 1 0 ___, 2H+
-0.41
(13.62)
- 0.82
(13.63)
Water do.:s not absorb visible light. but one could envision a sequence of reactions
a photosensitizer for the de.:omposition. The first step
that utilize [Ru(bpy)3f
woukl be absorption of solar energy by
(Ru(bpy),]2
Oculz. C. : Sulin. N. Pruc.
Chlm. 1980. S2. m1.
["Ru(bpy).,.Jl
A<aJ. S<l. USA 1975. 72.
Swin. N.: Crcusz. C.
J.; Sima. J. Ct>Ord. Cllmr. R ..v. 1990. 107. 1-212.
(13.64)
Appl.
564
13 Coonllnollon Chemistry: Reactions. Ki,...ics, ond Mechanisms
The excited state cation has the potential to reduce water.

2{*Ru(bpy),]2+ - > 2(Ru(bpy)3]l+ + 2e2e- + 2H20 - > 20H- + Hz
2[*Ru(bpy)3 ]2 + + 2H20
+ 20H- + Hz
--+
0.86 V (13.65)
-0.41 V (13.66)
0.45 V (13.67)
The [Ru(bpyhf+ generated in reaction 13.67 could then oxidize water.

2[Ru(bpy)3) 1 + + 2e- - > 2(Ru(bpy),J2+
HzO- 102 + 2H+ + 2e2{Ru(bpy)3])+ + H 20
--+
2[Ru(bpy),)Z+ + 102 + 2H+
1.26 V (13.68)
- 0.82 V (13.69)
0.44 V (13.70)
If we sum Eqs. 13.64-13.70 we obtain Eq. 13.61 . The absence of a ruthenium complex
in the overall equation reveals its catalytic nature.
In practice, however, the scheme fails for several reasons. FirSt, reaction 13.67 is
much slower than decay of [*Ru(bpy)3jl+ to its ground state. Second. the production
of one mole of hydrogen requires two electrons and the production of one mole of
oxygen involves four electrons, but the ruthenium complexes provide or accept only
one electron at a time. This means that various intermediates arise as the reactants
proceed to producls and the catalyst would be required somehow to stabilize these
intermediates while sufficient electrons are being provided. A variety of quenching
agents, both oxidizing and reducing, have been used in attempts to circumvent these
problems. The cycle presented in Fig. 13. 11 is an example of reductive quenching. An
electron is passed from [*Ru(bpy),f+ to methylviologen. MVH.
[*Ru(bpy)3J1 +
(13.71)
[Ru(bpy)1]>- +
Triethanolamine (TEOA) is added to the initial reaction mixture to reduce

(Ru(bpy)3] 3 + as it is generated; thus the back reaction (producing [Ru(bpy),.tl+ and
Mvz+) is retarded. The reduced methylviologen MY+ reduces water to hydrogen in
the presence of collodial platinum and is oxidized back to MV2+. thereby completing
the cycle. Many other cycles have been devised. some of which succeed in splitting
water into hydrogen and oxygen with visible light, but none of which are yet of
practical importance.9
The cleavage of water to produce hydrogen and oxygen is only one of several
photochemical redox reactions with major economic potential to be studied in recent
Sourus througll
ond Cotolys/s; Gtih zcl, M., Ed.; Academic: New York,
1983. Sec O'Rqan,
M.
199t,J.SJ, 737-74QforthcdcS(:riplionoCnncw aolnrcell
on T'o(h wi1h n monolaycroCRuL 2((S4-CN)Ru(CN)lih (l 2,2 '-bipyridine-4,4' -dicarboxytic
llcid; L ' 2.2'-bipyridinel. This inexpensive edt is more cffic:icntJhan I he na.!ur.ol aolarc:clbuscd in
pholosynthcsis aftcl shows great commcrct.l promise.
565
Meehoniamo of a..loa R.action
(\
docompos;tioft -
TEOA' \Ru(bp)l)j+
Ru(bpy):'
Rulbpyl!'
1EOA
H,o
Fig. 1111 A system for tt...

reduction o(
C1um. EJuc. lll83, 60. 882-887. Used wilh permission.)
H,
lo H:. IFrom Kutal. C. J.
times. Another is the reported reaction of nitrogen with water to produce amrnoniaso
(see Ch:lpters IS and 19 for further discussions of nitrogen fixation):
N2
...
--+
2NH3
+ f02
(13.72)
This conversion is catolyzed by [Ru(Hedta)(H20))- (Hedta = trianion of ethylenediaminetetraacetic acid) at lO c and 10' Pa in the presence of a solid semiconductor mixture (CdS/Pt/RuOz). The photocatalytic production of ammonia is
initiated by absorption of visible light (SOS nm) by the CdS semiconductor (Fig. 13.12).
Presumably, the incoming photons promote electrons from the valence band (VB) of
CdS to its conducting band (CO), a process that leaves holes in the volence band.
Water is photooxidized by Ru02 , releasing electrons which are trapped by holes in the
valence band of CdS. T he electrons in the conducting band are transfe"ed to the
ruthenium complex via platinum metal . Protons from the water oxidation are attracted
to the reduced ruthenium complex, interact with coordinated N2 in some unknown
Cashion, and are expelled as NH1 The cycle is complete when the coordination site
left by NH1 becomes occupied once again by H 20 . It remains to be seen whether
proposed cycles such as this one measure up to their promise.
Inner Sphere
Mechanisms
In ner sphere reactions are more complicated than outer sphere reactions because, in
addition to electron transfer, bonds nrc broken nnd made. S1 A lieand which bridges
so Khan, M. M. T.: BhaniWIIi. R. C.;
C. Alfln-1. Otcm. /111. &1. /!nal. 1918,17, 92l-9U.
Chcm. tfll. 10, m. Endicon,J. F.; Kun...r, K.; Ramasaml, T.; Roezinscr,
F. P. Prog. mor,. Clwm. l fll, JO. 141-tl7.
" Haim, A. Pror.
two metals is intimalely involved in the electron transfer. Tile classic example of this
type of mechanism was provided by Taube and coworkers.n Their system involved
the reduction a cobalt(lll) (in (Co(NH,),CI] 2 +) by c hromium( II) (in [Cr(H20)J 2 +)
and was specifically chosen because (I) both Co( Ill) and Cr(ll l) form inert complexes
and (2) the complexes of Co(ll) and Cr(ll) arc lnbile (see page S49). Under these
circumstances the chlorine atom, whac remnining firmly attached to the inert Co(IU)
ion, can displace a water molecule from the labile Cr(ll) complex to form a bridged
intermediate:
[Co(NH 3))CI]2+
+ [Cr(H 20)6J2 +
--> ((H 3N),Co- CI-Cr(0Hz),J+
+ H20
(13.73)
The redox reaction now takes place within this dinuclear complex with formation of
reduced Co(ll) and oxidized Cr(lll). The latter species forms an inert c hloroaqua
complex, but t.h e cobalt(ll) is labile, so the intermediate dissociates with the chlorine
atom remaining with the chromium:
(13.74)
The five-coordinate cobalt(ll) species presumably immediately picks up a water

molecule to fill its sixth coordination position and then hydrolyzes rapidly to
[Co(H20)6J2 +. Formally, such an inner sphere reaction consists of the transfer of a
chlorine atom from cobalt to chromium, decreasing the oxidation state of the former
but increasing that of the latter. In addition to the self-consistency of the above model
(inert and labile species) and the observed formntion o f a chlorochromium complex,
further evidence for this mechanism has been obtnined by running the react ion in the
presence offree radioisotopes of chloride ion in the solution. Very little ofthis labeled
chloride is e ver found in the product, indicating that the c hloride transfer has indeed
been through the bridge rather than indirecUy through free chloride.
(Ru(
2NH,"'
H,O
. !2
JH,O
Fig. 13.12 A system for the photodlcrnical conversion
to NH,. Electrons (c:-) oce
promou'd to the: conduction band (CB) k:lvi111 holes (h 1 in the: valence band (VB). IModilie<l
R. C;
C Angtw. Chrlrt. IM. Ed. Engl. t988. 27,
from Khan. M. M. T.:
923-925. Reproduced with pc:rmis.Wn.J
-- -----
Taube. H.; Myers. H.; ltic:h. R. L / . Am. Owm. S. ttsJ, 7J, 4tt8.
Mech011isma of Redox R.ac:lions
Table 13.9
Rote COOIII..,Is for !he
witlt
ezl+o
NH3
8.9
ow
r-
I.S X Hf
Z.S x 105
H20
ei-
Br-
1N)
o.s
6
1.4
3
10-S
to'
to'
t06
to'
Ba.solo, F.; Pearson. R.

G.
of
Inorganic
2nd
cd.: Wiley: New Yorlc,

1967.
567
1be importance of the nature of the bridging ligand in an inner sphere reaction is
shown in Table 13.9. The reduction of [Co(NH3>,c!f+ is about 1010 faster than the
reduction of [Co(NH 3)tf+. The bound ammonia ligand has no nonbonding pairs of
electrons to donate to a second metal. Thus the reduction of the hexaammine complex
cannot proceed by an inner sphere mechanism. If ligands are not available which can
bridge two metals, an inner sphere mechanism can always be ruled out. A second
important feature of an inner sphere reaction is that its rate can be no faster than the
rate of exchange of the ligand in the absence of a redox reaction, since exchange of the
ligand is an intimate part of the process. As was noted earlier, electron transfer
reactions must be outer sphere if they proceed faster than ligand exchange.
It is often difficult to distinguish between outer and inner sphere mechanisms. The
rate law is of little help since both kinds of electron transfer reactions usually are
second order (first order with respect to each reactant):
rate
J.toxidant][reductant)
(IJ .7S)
Furthermore. although the chloro ligand in Eqs. 13.73 and 13.74 is transferred from
oxidant to reductant. it is not always the case that the bridging ligand is transferred in
an inner sphere reaction . After electron transfer takes place in 1he dinuclear complex,
the subsequent dissociation may leave the ligand that functioned as a bridge auached
to the metal with which it began."' If the britlging ligand stabilized its original
more than the newly formed complex, failure of its transfer would be no surprise. For
example:
(13.76)
Presumably the C-bound cyano group stabilizes the tf> (FeZ+) configuration of
[Fe(CN)J'- more than the N-bound cyano group would stabilize a d 6 (Col+) configuration in [Co<CN),CNC))1 - .
If the bridging ligand contains only one atom (e.g.. Cl- ). both metal atoms of the
complex must be bountlto it. However. if the bridging ligand contains more than one
atom (e.g .. seN-). the two metal atoms may or may not be bound to the same
bridging-lit:antl atom (see Problem 13.30). The two conditions are calkd adjacem and
unrott: :utack,
A remote attack may leatl to both linkage isomers:
In the above instance the kinetically ravored nitrito complex isomcrizes to the the"'
motlynamically favored nitro complex in seconds.
SJ The r:llc-.Jclcnninin& slep in most iM<r sphere rcac1ions is 1hc
transfer step. no1 the
formation olthc bridsed <OITC'Icx. If dissociation or a reaclllnl compte: were rate detcnninin& lnt
onler kinetics would be expcCied.
,. Hllim. A. Prog. lnorg.
19&3. JO, 213-3S1.
568
llCoordinotion Chemi.,.: Reactions, Kinetics, and M.chonisms
Mixed Volence
Complexes
Theoretical treatments of electron transfer between two transition metal ions in

solution are complicated by contributions arising from solvent reorganization and by
transfer pathway uncertainties. If, however, the reducing and oxidizing agents are
separated by a bridge within a single bimetallic complex, there will be no solvent
molecules between the metal ions and the pathway will be defined. Furthermore.
electron transfer over various distances can be studied by varying the length of the
bridge and this can provide some insight into important biological processes. Complexes that contain a metal atom in more than one oxidation state are referred to as
mixed valence complexes. One could envision some systems in which the two metal
ions are so far removed from one another that electron transfer does not take place nor
can it be induced:
M2+---MJ+
In other systems the two metal ions may be so strongly coupled that properties of
the separate + 2 and + 3 ions are lost and the entire unit is best represented as two
+2l ions.
M2''>+ -
Mz'<>+
Of greater interest are systems in which modest coupling exists between metal
centers, for in these it is possible to photolytically induce electron transfer. The
potential energy diagram in
13. 13 shows by means of a vertical arrow the
photochemical energy necessary for an electron to pass from the potential energy
surface of M2 + -MJ+ to the potential energy surface forM)+- M2 + . This means that
intervalence transitions are observed in the electronic spectra (often in the nearinfrared region) of these complexes but are not found in the spectra for monometallic
complexes of either M2+ or M1 + .l$ Of course the electron could also pass thermally
from one surface to the other, as for outer sphere electron transfer, through equalization of orbital energies by vibrational elongation and contraction of metal-ligand
bonds. A comparison of optical and thermal electron transfer is shown in Fig. 13. 14. In
the optical process depicted in the top part of the
we see that transfer occurs
prior to bond length adjustment, but in the thermal process (bottom of diagram), bond
length changes take place (as required by the Franck-Condon principle) prior to
electron transfer.
Fig. 13.13
enef"gy diagram ror a

pholochemicaly induced
homonuclcu electron
transfer in a mixed valence
complex (R
reactants;
P ; products).
Nuclear eonligu:ration
ss A tiaht ion pair may also give rise to a mixed valence transition.
569
Mecho11is.,. of ltedoa leom0111
fig. 13.14 A comparison oC photochemical and thermal electron lnnsfcr processes in mixed
valence systems. The photochemical pnthway (top) allows electron lrnnslcr prior to bondlenath Adjustment, while the lhennal route (bottom! requires adjustment prior to electron
transfer. (Creutz, C. Prog. l norg.
1983, JO, 1-73. Used with permission.)
One photoactive system which hos been extensively studied is a bimetallic complex of Rul+/R.Jl+ in which 4,4'-bipyridinc functions as the bridge.
((HJN)5Ru1 - N Q ) - @- Rul+(NH;,),) -
@-@-
(13.18)
Ru1(NH,),
An absorption ( IOSO mm) found in the ncar-infrared spectrum of this complcK arises
from a miKed valence transition . Light-induoed metal-to-metal cttarse transfer was
predicted by HusbS6 for systems of this type before it was observed experimentally.
Further, his theory relates the energy of absorption to that required for thermal
electron transfer (hv = 4 x 0 ) and from this it is possible to calculate the thermal
electron transfer rate constant (S x J()l s- 1).S7
The expectation that the rnte of electron trnnsfer will slow with increasing distance between the two ions is rcnli7.ed, as shown fo r [Ru(bpy>tCihL- L complexes in
Table 13.10. Distance alone, of course, does not determine how quickly an electron
can pass through a bridge. The nature of the bridge itself is important with some
bridges being more resistant to electron transpor1 than others. A comparison of the
diphosphine and pyr:u:ine bridges, which are nearly the snme length, shows the rnle
constant of the latter to be 30 times that of the former.n
Applicotlons to
Bioinor gon ic
Chemistry
Cytoch+"ome c. discussed more extensively in Chnpler 19, is an important biological

intermediate in electron transfer.s9 This metalloprotein. found in all cells. has a
molecular weight of approximately 12,800 and contains 104 amino acids (in ver1e""Hush. N. S. Prog. l r!CNf. Chi!'". 1967, 8, 391-444.
" Brown, G. M.; KrenUien, H. J.; Abe. M.; Taube H. lnorg. Cllm. 1979, lB. 3374-3379.
'"Creutz. C. Prog. l nDfB. Cht!m. 1913. JO, 1-73.
,.. Slnld. Bondinr (Bn1in) ' " ' 7l tentire ootume Is de\'Oied to "L.ona-Ranac Electron Tr:>nsl'or in
BiolosY" ). E1c1r011 Transfrr in lrmronic and Blolorical Syr,ms; Bolton. J. R. ; Ma13p, N.;
Mcl.<ndoa, G .. Eels. ; Advonccs in
228; Amerielln Olcmical Society: WllshiinaJon, DC..
1991. Mct.endcn, G. Ace. Clwm. R 1918. 21, 160--167. Mon:w, R. A.; Sutin, N. Biochim.
Biophys. Aria 1915, Bit, 26>32:2. Bowler, 8 . E. ; Raphllel, A. l..; Gray, H. 8 . Pro(f. ln<q. Clwm.
199t.J8. 2l9-l2:2.
S. l..; Elis. W. R. , Jr.; Cruldllcy. R.. J.;
H. B. SO,nct986. lli.
943-9S2. Scott, R.. A.; Mauk.A. G.; Gny, H. B. J . CMm. Ed..-. 1!115,61, 932-938. Mct..ndon,G.;
Guatr, T.; McGuire. M.; Simolo. K.; SII'1WCII. S.; Taylor, K. Coon/. C/lm. R.v. 1915.64. lll-124.
Sykes. A. G. Cl.,m. Br. 24, 1m. SSt- S54.
570
13COCM'dination ChiHTiislry: Reactions, Kinetics, ond Mechoni1ms
Tahle 13.10
Calculated rate constants
lor .a.crr- transf.r ;.,
(Ru(bpy}.Cihl-l
a>mf>le- and - -.. (t}

separating the metal
canters0
r,A
l- L
NON
Ph
'
Ph/
lr. .-
6.8
10 9
7.1
t x
ro
6.0
1010
11.3
tO'
13.8
107
Ph
'Ph
/'...
@-
H
N@-!=T-N
H
Creuu. <;. Prog. lnorg. Chrm. 1983,30. t-13.
bmtcs). It is an electron carrier for oxidative phosphorylation. tr.snsferring electrons

to 0:. The energy released in this process is used to synthesile ATP. The heme group
of cytochrome c lies near the surface of the protein. The iron atom is six-coordinate,
with bonds to five nitrogen atoms (four from the porphyrin, one from a histidine
nitrogen) and one sulfur atom from a cysteine. Since all six iron coordination sites are
occupied. direct electron transfer to iron is not possible, and the electron must pass
through the surrounding protein bridgework (see Fig. 19.3). Electron transfer rates
between horse heart cytochrome c (very stable and commercially available) and many
transition metal complexes have been studied. For example, the observed rate conslant for reduction by (Ru(NH))J 2 + is 3.8 x 104 M- 1 s- 1 which compares well with
the: value of 7.8 x 104 M- 1 s- 1 calculated from the Marcus cross-reaction
Calcula1ing rote constants for electron transfers h<twun two metalloproteins is a
much more complicated affair . Distances between metal sites of two such proteins are
often llll'ge ;md uncertain. A clever approach to gaining information about the distance
dcp.:mlence of electron tmnsfer in these systems is to bind a second metal center to
the surface of a single metalloprotein. A number of different electron transfer proteins
(including horse heart cytochrome c, cytochrome c,,.. azurin. plastocyanin, and an
iron-sulfur protein) as well as sperm whale myoglobin have been modified by attaching [Ru(NH 3) 5]2 + to a surface histidine nitrogen atom. The distance between metal
centers is thereby fixed and can be determined. In cytochrome c, for example. both
the Ru of the surface (Ru(NH 3),Hist and the heme Fe begin in the + 3 oxidation
state. The ruthenium moiety is reduced to (Ru(NH 3) 5Hisr chemically or by pulse
r.ldiolysis. The transfer of an electron from Ru2+ to Fe3 can then be followed by
monitoring the decreasing Ru2+ absorption. Since, in general, several surface histidine
nitrogen atoms are available for binding, it is possible, within the same protein. to
place (Ru(NH 3) 5:f+ units at various distances from the heme center. In fact four
different [Ru(NH,>5f+ derivatives of sperm whale myoglobin have been characteriled
(Fig. 13.15). ll turns out that there is generally an exponential dependence of electrOn
Mecha nis.,. of Red- ReaC1ians
571
Fig. 13.15 COI'I1fl'Jiel"

view of the heme
aroup and four rutheniu.m
auffoce histidlnes in spe>mwllale myo&Jobin. Oosest
heme-a,-Ru( His) edge-toedae distances are t4.6
(His48), 19. t (His81l. 20. t
(Hisll6), and 2:!. t A

(Hist2). (From Mayo,
S. L.; Eltis. W. R. J r. ;
CTUtchley. R. J.: Gray,
H. B. Sci,nu 1986. lli,
948-952. Used with
permission.!
tmnsfcr rntcs upon disumce in these sorts of systems ..., However. not all pathways are
identical so it is possible for a panicul:lt situ:11ion to be a n e:<ccption to this rule. A
theory has been developed th:lt suggests that e lectron tr.msfer in proteins is regulated
by pathW:Iys that arc optimal combin :ltions of through-bond, hydrogen bond. :lnd
through-space links. Acconlif18 to this moocl. the ( lectrun transfer will foUow the
best overalllinkage.62 Hytlrogen bond bridges will be less efficient than through-bond
linkages. but much better th:ln through-space electron tmnsport. Thus the optimum
will be the one wit h the best compromise or minimizing distance (covalent
and avoiding, if
hydroscn bond linkag(S a nJ . especially, throughsp;lCe gaps. These optimum pathways cun be computed makins usc of assumptions
about th( relative dli:ctivencss or throushbonJ. hy.Jrogen bon.!, ami through-space
links. Figure 13. 16 illustrates s uch a pathw:ty.
The d riving force of a reaction, as noted earlier und as pre.Jicted by Marcus
theory. also affects the mte o( electron transfer in und bet ween proteins. Replacing the
heme in a ruthenium-modified myoglobin with another metal system give s one a
chance to evaluale these effects. When the heme is replaced with a photoactivc
palladium porphyrin, which is a good reducing lij;Cnt in its e lectronic excited state, the
electron transfer driving force
S tudies such as these allow reorganization
energies, which strongly influence reaction rates, to be evaluated .
"'AlWp. A. W.; Albin . M.: Moyo.S. L :Crutt.hley. R. J.:
H. D. 1. Am. Chtm. Soc. 19SI, //0,
43S-439. Cowan. J. A.:
H. B. lnoflt. CArm. t!lll,, 18, 1074--20711.
Bc:r:uan. D. N .; Onudoit. J. N. PhototynlhiAis Rtucrrh t ,.,, 21. 17}-t86. Beratan. 0 . N.;
Onuthic. J. N.: BetU. J. N.; Bov.ier, B. E.; Gray. H. B. 1. Am. Ch,m, Sor. t990, 1/2, 791S-192t.
In m&ny
the c:k<:tronie IUnndina pouhway is onaroaoua 10 vuriolon electric c:lrroits with
dilfererJ resistors: Tbc lonp
"circuit" in these
o.hc PQitt
rni>lanu. Hydroetn
bonds tc:nd to ictcru1Se ruiltance and open spece hlos the greatesl ot al.
6J Kans. J. L; Lieber. C. M.; Gray, H. B. 1. Am. Clwm. Soc. 1,.._ 1/0, '99-{,00.
62
572
13 Coordiatia a...,.istry: Reactions, Kmetlcs, and Medlaftismo
Fig. 13.16 Alternative

pathways
electron
rrom ruthenaled His62 to
lhe heme in a mutant yeast
cytochrome c . [From
Bowler. B. E.; Meade.
T. J.; Mnyu, S. L.;
Richard. J. H .; Gray, H . B.
J . Am.
Soc. 1989,
Ill , 81S1- 81S9.

Reproduced wilh
pcnnbsion.J
Problems
13.1 MeW-hAlogen bonds arc more labile than mcW-t.itroaen bonds. Use this inronnation and
the lrans cfl'cct to devise syntheses r the roUowlna geometric: isomers rrom (PtCt.J'-.
a.
a....._ ,......er
a....._ ,......er
b.
.,.,Pt..._
Py
NH3
H3N
.,.,Pt..._
Py
13.2 Predict the aeomdries or the complexes which result rrom the rollowiRA reactions:
(PI(NOJC1,) 2-
+ NH, ---+ (Pt(NO:J(NH3)CIJ- + ct-
b. cis-[Pt(RNHJ.(NH ,)(N01)]
+a-
---+ Pt(RNH 1)(NH3 )(N0 2)CI
+ RNH 2
13.3 Predict the products of the rollowina reactions (I mol or each reactant):
a. ( P I(CO)CI3] - + NH3 - +
b. (Pt(NH,)Br,) -
+ NH,
---+
13.4 Trialkyl pho>phines are rather aood trans directS and, as expe.:ted . the reaction or Bu3 P
with [Ptct.J1 - lives the trans isomer n a ma,jor product. However, when one uses Ph1 P in
this reaction. only the insoluble cis product is obtained. ()ll'er an explanation for this
Al)patent violation of the trans-ell'cct prediction. (Problem JJ.S may be helpi\JI.)
IJ.S When pure
occurs to live a mixture
is placed in $0llltion with a 1race or Bu,P. isomerization

or cis uncl lrans isomcn. Provide a plausible mechanism.
13.6 Nickel complexes are observed to underao substiiUiion much (liSter lhan platinum complexes. Ofl'u an explanation.
13.7 The rollowil'18 data were colleclcd r the reaction (ellen

HN(CH,CH1 N HthJ:
[Pd(cllen)SCN)+
py -
(Pd(cllcn)pyJ'
+ SCN'"
dicthylcnctriamine.
Probl-s
573
[py)
6.6 )( 10-3
8.2 )( 10-)
2.s
10-2
1.24 )( 10- 3
2.48 )( 10-3
1.24 )( 10-1
Use lhe data to calculate k 1 and k2 fer substitution in this squace planar complex.
13.8 Skdch plots
versus [YI ror two cases of subSiitulion of a square planar complex:
(a) one in which lhe solvenl pathway is insignilk:anl and (b) one in which lhe SOlvent
pathway is exclusive.
13.9 The rale of SllbSiitution in a square planar complex often depends on the identity of I he
leaving group. X. For the reaction:
(Pl(dien)X] + py --> (Pt(dienJpyf
+ x-
lhe following da ta were collected:
(s-t,
ligand, X
H 20
a-
,-
Br-
NQi
cw
1900
3S
23
10
0.05
0 .017
Ofll>ese liaands. CN- has the least efrect and H20 has the areatest elrect on lhe rate of lhc
reaction. Yd as 1rans directors,jusllhe opposite order is observed for lhcse two ligands.
Explain.
13.10 The hydroxide ion is a stronger base than ammonia, and yet it reacts more slowly than
ammonia with a square planar complex. Explain.
13.1 J Rationalize the order of the followina k..,. values for the reaction of cis-Pt(PEt,jzLO with
py.
o-tolyl
0.08
0.0002
mesityl
0.000001
phenyl
13.12 Skdch a reaction profllc for substitution in a square planar complex in which (a) a live
coordinate intennediate exists. but bond breakina is more important than bond making:
(b) a live-coordinate intermediate exists, but bond makina is more important than bond
!nakina.
13.13 Substitulion reactions of dinuclcar platinum( I) complexes have been investigaled ... The
rate constant for the reaction below is 93 :!: 20 ,.-
at JOC in dichloromethane. Rale
constant fur halide stbstitution in
complexes are typically
M- 1
s-
s-.
.. Shimun. M.; Espenson. J. H. tnorz.
1984. 2), 4069-4071.
ao-
57 4
13 Ca ....dinatian Chemislry: Reactions, Kin .tics, and
1>t.' 21p
PPII.
Br-Pt-Pt - Br +Ct" - - - er-Pt-Pt-a +
PPhz
Ph.P
er
PPh2
Cornman on Jhe 1r.ms el!"ecl exhibiled by lhe PI- PI bond.

13 . 14 The platinum-carbon NMR coupling constants for lrans[PI(PEt,),(COlHr and
lruns-[PttPEt,),(CO)Df+ are 996.2 j: 0.6 and 986.3 x 0.6 H z. rc.s pectivcly. Discuss the
rela1ive 1rans influences o f H and D."'
13 . 15 When (PI(NH 11.1,. is ullowcclto s10nd inO. I M HO for many d;sys 81 JOc. no reaction is
observed. Only under forcins conditions is lhe cation convened to rransPI(N H1),CI 2
However. when (1'10.] 2 - is trcAJed with NH,. substitution 10 aive cisPI(NH,l:!(:l: is
npid."" Acc:oun1 for t he dilferencc in the rates of these 1wo reactions.
13.16 In Jhe syntheSis of c/.f'{PI(Me1SI:(NH,l:J2 from cis-PI(NH,),CI,, the rcacl:lnt is first
Jrea1e<l with A,gCIO and 1hcn wi1h
What role does saver perc:hlorolc play in this
re:k:tion?
13.17 For the reaaion:

[Pd(L IOt
+ y- ---+ [Pd(L )YI + 0"
lhc followinc data were coUwed:07
OH- 1,4,7-Me,dien 24.9

OH - J,I ,7,7-Me4dien 0.90
1-
1,4,7-Me,dien
1-
l , l,7,7-Me 4dien
21.9
0.99
- 12.2
- I.S..S
-9.2
- 13.4
223
4.Sl
4318
+21.1
+2S.2
-18.9
0.28
Accoun1 for Jhe foUowi111: (a) Diii"C1"ences in k 1 ond k: values for Ole auack of substr.ue b y
y-. (b) Dilferences in VOlumes or DCiivalion for . - arK! OH - .
13. 18 Skelch cnc'l}'/rcaction coordinule diOVol"lt for
prO<Iucl5 ore more stable than rcac:lllnt. and
rcocl ions in whi.:h
a. no intcrmcdiute is formed.
b. an imermediule is formed and bond brenkina and bond mulcina arc equally imponont.
13. 19
c. 11n intcrmcdiate is formed and bond
is more impon ant than bond
d. nn intcrmedillte is formed and bond breakina
i5 less important than bond making.
the foUowifll in order or inereasina rate or water cxchanae:

[VCH:OJ..J>+, [Cr1H,O),j+, [MalH:Oit.J'+.
13.211 a.. The rate ol
exchanac for (MO{H20lr,IJ is very slow. Why'!
b. The rate constanl for the formation ol(MO{H,O)..(NCSlf+ at 298 K is O.J 17 M- 1 s

a,nd for (MO{H,OJsOf is 4.6 x to-J M- 1 ,-. Scven-coordinllte molybdenum(lll)
"'CroblrCC, R. H .: Habib.. A. lnt>'l/.
t9U. JJ. 3696-M99.
.. Annibale. G.; Clnowsc, L; Calcalini, L : Maranacni. C .: Mlchdcco. G.: Tube, M. L lntJTJl. Chern.
1984. 21. Z70S-270S.
01 Brcel. E. L 1. ; van Eldilc, R.
Chtm. 1984,21. 186S-1869.
Problems
575
complexes are known. The volume of uclivntion for the NCs- renction is -1 1.4 em'
mor-. Explain how each of the factors SUQ8esls thatlhese anntion reactions proceed
by an 1., mechnnism. (See Richens, D. T.; Ducommun. Y. ; Mertuch. A. E. J . Am.
Clrrm. Soc. 1987. 109. 603-604.)
13.21 The rate consumt for the nquation of JCo(NH,Me)sCI]2 + is 22 times larger lhlln for the
aquation of [Co(NH3) 5Cif+. Provide an explanation. For anntoaous chromium complexes
the rate consiUnt is larger for the ammine complex than for the methylamine complex. The
explanatioo for !he revcrsnl is controversial. Read Lay. P. A. lnorr. Clrem. 1987. 26,
2144-2149,nnd sunvnuriz.e argumenlS for and against an 1. mechanism for the chromium
complexes.
13.22 The hydrolysis of chela ted Cllfbonnto complexes of cobalt( Ill) is much fasoer in acid lhnn
in neutral solution. Explllin.
13.23 The reactions of [M(H 20),JH (M Zn and Cd) wilh 2,2'-bipyridine have bun soudietl.
For which metal is !he reactio n most likely to proceed by an associative interchange
mechanism? (See Ducommun. Y. ; Luurenczy. G.; Mertach. A. E.llforfl. Chem. 1988.27,
114&-1152.)
13.24 W<tte'r exchange by dissocia1ion becomes increasingly importunt for bolh [MtH: Ol6 f
and (M(H 101,r as one move$ from left to right in lhc periodic table. Explain.
13.25 The ouoer sphere electron exchange reaction:
is 200 times foster t.han ohe reacoion:
Account ror ohis difference by giving ;on cvalua1ion of l hC relative importance 1:1: lhe
(I)CIOfS cnnoribuoing to the energies of acoivution.""
13.26 Ligand exchange in I Fctphcnl,J,. and in (FelbPYhf is much slower than lhe transfer or
an tiJrcln from the bipyridine complex to ohe phenanthroline complex. Why
this
rule out an inner sphere mechanism for the electron trnsfer?
13.27 Calcuboe k 1: for 1he reaction:

Fe3 (aq) + (RuiNH}lt' -
Fe'
(nq}
+ [Ru<NH,I.t'
rates ror
oxitl;ono anti rcductano arc
M- 1 s- and '-tl x
respectively. Th\! cquiliboium cnnsmnt for the reaction i
x IIi'.
IJ.lll The (Col H:OJ..I' ., >'
by
to' M - 1 , - .
exchanJ.{c re....:oion pmcccds 10 ' times fa.'<Jcr I han prodictcd
&he Man:us cqualion. Wholl
1hls suggest about 1hc mct:hanism
or
clcc1ron
tmnsfer"!
13.211 The re3Ciion:
(Co(NH,)50H)'+
+ (Cr(OH:J.]'
___, (Co(NHJ)sOH]
+ (Cr{OH,)6 ] '
proceeds rapidly (k I.S x 101 by an iMer sphere mechanism. When OH- is replaced
by H,O in the cobah reactant, the reaction slows considerably (k 0. 1). his observed ,
however. thutthe reoc1ion rate is inversely dependem upon lhe concentration of hydrogen
ion. Provide an explanation thnt is oonsisoena with these lllcts.
13.30 When (Co(NHl),SCNI' reacts wioh [CriOH: l,,J' . bolh
and
ore producctl. II hAs been pestul:ued 1hn1 both remote and
adjacent
nrc involved in the fonnation or these products. Dr.IW britlgins intermediates consistent with this view for 1he formation of bo!h products ...
.. Bernhard. P.; BUrgi. H.-B.; Houser. J.; Lch11111m. H.: t..udi. A .lnufl/. Orem. 1982.21.3936-3941.
.. Haim. A. PrOIJ.
tnorr.
1983. JO. 273-JS7.
$76
13 Coordinorion Cheraistry: Reoctions, Kinetic:t, and Mechanisms
13.31 If renc1ioo IJ. 76 proceeds by an inner sphe<e meclumism with the formation of
((NC),Fe-C;;;;;;N--co(CN),J"- as an inlennccliale, what cnn you say nbou1 the r.ue of
Fe-C bond breakina relative to the rate of Co-N bond breaking?
13.32 The reaction or CrH with
in the presence 0( acid inilially gives
NH,
Can we conclude that this reaction proceeds by remote attock?'
13.33 Deline the fottowina terms: fluorescence,

cence, and chemiluminescence.
phocolumines-
13.34 If I mol or 4.S2-nm photons are absort>ed by (RU(bpy),)'+. how many U are ab$orbcd?
How many cV docs this correspond to? tr [Ru(bpy))t tics 2. 1 eV higher in enerJY than
what wavelcr1gth 1:1
wiD be emitted when Ihe excited state relaxes to
the ground state?
13.35 What wavclenath oftiaht would be needed to provide the minimum energy for the reaction
N:t(g)
JH,O(I) -
2NH,(g)
iQia)
for which l!.GO ; 678 kJ mol- 1?

13.36 The inrervalcnce apectnim of
consists of an abaorptioo at IOSO nm. In what
part or the electromagnetic spectrum is it found? Explnin how 1his ab$orptioo arises.
13.37 A cyctic: voltammogram
in acetonitrile is shown below."
v
How do you account for the observation or three reduction potentials?
13.38 lr the poccntiata for Eqs. 13.62 nnd 13.63 had not been given, could you have calculated
them (Chapler 10)?
70Taube. H.; Gould, E. S. Ace. CMm. Rn. 1969. 2.321-329.

71 Juris, A.; Bahani, V.; llari&ellc!ti, F.; Campagna, S.; Belser, P.; von Zelcwsky, A. Coord. Chem.
1988.84.85-271.
Chapter
14
Some Descriptive
Chemistry of the Metals
In the preceding chapters principles guiding the structure nnd reactions of transition
meul complexes have been considered. The present chapter will concentrate on the
propertjes of individual metals in various oxidation
The stabilities of these
oxidotion states will be examined and the similarities and differences compared. 1be
moterial in this chapter and much of the next may be characterized as the "'descriptive
chemisll)'" of the alkali. alkaline earth. transition, lnnthanide. and actinide metals.
Unfortunately. descriptive chemistry has not always been especially popular with
students and teachers. Admittedly. complete mastery of all the properties nnd all the
reactions of the compounds of one element would be an impossible task. to say
nothing of attempting it with 109. Furthermore, new reactions and properties are
constantly being discovered that require the continual revision of one's knowledge.
Nevertheless, it is impossible to ignore descriptive chemistry nnd try only for mastery
of the theoretical side of chemist.ry. Theory can only be built upon and c!Jej:ked
against facts. Actually, in reading this book you will encounter a vast body of
descriptive chemistry, perhaps without consciously being aware of it. As each theory
or model has been presented, an appeol has been made to the real world to support or
modify that concept. Much of this descriptive chemistry may go unnoticed, but
consider that almost all metal carbonyls are diamagnetic (Chapter IS), that magnetite
has nn inverse spinel structure (Chapter I I), and that potassium permanganate is
purple (Chapter II ) or that it is a strong oxidiz.ing agent (Chapter 10). Furthermore
(Chapter 13),
(PtCIJ2 -
+ 2NH 1
ci.rPtCI:r(NH,)2
+ 2C I-
(14.1)
When it comes to what is "i.,..,ortant" descriptive chemistry, chacun tl son goOt!'
lhe so-c:atled
on. mus1 pN:k and dloose which racts
are 10 be prQenlcd. The reader sllould beccme familiar with tine sdS of vdo.rnes oa inorpnic
dlcmislt')': Cump<tlwnsi"t C<>ordi-ion Clwmhtry; Wilkinson, G.; Gillard. R. D.; Mc:CleYCny,
J. A. Eels.;
Olllord. t9S7. COtfiP'thltUIYI lrror,nic Clwmistry; Bdar, J . C . Jr.:
Emdbos. H. J .; N)'llolm. R.: Trocmu-Dickenson. A. F .. Ed-. : Perpmon: Oxbd. t973. MTP
lrrtnnatitJMI R,WW ofScimcr. /rrortDIIic Clvmhtry; Etndbls. H. J., Ed. ; B..terwortha: London,
1972. t975; Series 0... and Two.
' This is why any sint!lc 1101ume.
577
578
14
s- Descriptive Ch...,is try of tloe Metols

Even so. it sometimes seems as
no facts are retained. Each of us has a
"silver chloride is a pale green gas'' story. Our local one concerns the organic
graduate student who reported that he couldn 't get bromine to dissolve in carbon
tetrachloride (!). He even tried grinding it with a mortar and pestle (!!). When his
professor invest.i gated, il turned out thnt the brominr was still in an unopened container in the botlom of the packing cnn, and the materiol in question, being subjected
to grinding and solubilization tests, was lhe vermiculite packing material (!!!). Truly.
A lillltt learning is a dangerous thing;
Drink deep, or taste not the Pierian spring.z
In this chapter the theories developed previously will be used to help correlate the
important facts of the chemistry of groups 1- 12. Much of the chemistry of these
elements, in particular the transition metals, has lllrcndy been included in the chapters
on coordination chemistry (Chapters II , 12. and 13). More will be discussed in the
chapters on organometallic chemistry (Chapter 1.5), c lusters (Chapter 16), and the
descriptive biological chemistry of the tronsition metals (Chapter 19). The present
chapter will concentrate on the trends within the series (Sc to Zn. Y to Co.!, Lu to Hg,
La to Lu. and Ac to Lr). the djffcrences bet ween groups (Ti- Zr-. Hf; Cu - AgAu), and the stable oxidation st:ltes of the various metals.
General Periodic
Trends
As the clfec.tive atomic number increases across a series of tronsition metals. the size
from poor shielding by the d electrons. For transition metal ions the results
of ligand lickl effects override a smooth decrease and so minima in the ionic radii
curves are found for d 6 low spin ions, etc. (F"IB 11. 1.5). The decrease in ionic radii
favors the formation of stable complexes, and this, tosether with ligand field stabilization energies (LFSEs) arising from incompletely filled d oroitals, is responsible for t.h e
general order of stability of complexes. The increasing availability of d electrons for
back bonding via 11 orbitals (especially in low oxidation states) increases the softness
of the metal ions in going from len to right in a scriu. However . the J orbitaJs in ions
2
such as
+ and Zn have become so stabilized that rr bonding for them becomes
re.lntively unimportant.
The d ifferences between one series and another are discussed later in this cha pter.
but we may note some seeming paradoxes: The heavier metals tend to be somewhat
less reactive as elements. and yet they arc more easily oxidized to higher oxidation
states; the first and second series appear to be more closely related 10 each other than
to lhe third on lhe basis of ionization energies. and yet it is common to group lhe
second and lhird series together on the basis of chemical properties and to dilferenliatc
them from the first series.
The first ionization energies of the main group and tronsition metals are listed in
Table 14.1. The first two series do not differ significantly from each other-sometimes
an element of one series is higher, sometimes the other. Bcsinning with cesium the
third series has a noticeably lower ionization energy as we might expect on the basis of
Pope. A. An E.ssoy on otliciJm. hit II, I. 15. Sec Banleu. J. Fomililw Qw>tations: 8edt. E. M .
Ed.: Uuk. Brown: llcton. t968: p.coob. Ewns. B. Dklionoryuf(}wtotiDn: Bonanm Boob: New
Yorlc. 1961!: p 381:10.
Ge.,.rol P.noclic Tr ends
579
Tobie 14.1
Ground ttate ioniatian energies of the main group oncl tranoiti"" metals in kJ .,.,r (eV
,.,..,....,
lA
(1)
IIA
(2)
1118
4th period
4 19
(4.34)
590
(K- Zn)
(6.11)
Sth period
(Rb-Cd)
6th period
(Cs- Hg)
403
550
(4.18)
376
(3.89)
(5.70)
631
(6.54)
616
(6.38)
538
(5.58)
Gr001p
(3)
503
(5.21)
Moore, C. E. loniwrion Por.ntiDh

Nntlotd Bureau of StandArds: W11$hinJton,
IVB
(4)
VB
(5}
VII
(6}
658
(6.82)
660
(6.84)
654
650
(6.74)
(6.17)
(6.79)
VIII
(7)
653
664
685
702
(7. 10)
(7.28)
760
(7.88)
770
(7 ..98)
VI liB
(8)
717
(7.44)
(6.88)
761
(7.89)
mor')
(9)
159
158
(7.87)
71l
(7.37)
840
(8.7)
(7.86)
720
(7.46)
[10)
(8.34)
746
(1.73)
731
(7.58)
880
870
890
(9. 1)
(9.0)
(9.22)
Umlls Derird/rom tht Analyses of Optical
737
(7.64)
18
(11)
805
JIB
(12)
906
(9.39)
(9.00)
1007
(10.44)
NSRDS.NBS 34;
DC, t970.
larger size (Cs > Rb, Ba > Sr, La > Y) . A reversal of the ionil.ation trend, beginning
with Hf. occurs after the lanthanides are added. The addition of 14 poorly shielding 4f
electrons and the enhanced importance of relativist.ic effects results in increased
ionil.ation energies and decreased size. The "lanthanide contraction" and other
phenomena related to it are discussed in the chapter on periodicity (Olapter 18), but
for now we may n<lle that atoms of postlanthnnide metals are ( I) smaller than would
otherwise have been expected-so much so that they are often essentially the same
size as their liGhter
ond (2) more difficult to oxidize. The l:llter phenomenon
proceeds with ever increasing ionization enercies until the mD!>t noble metals are
reacheo.l : iridium, platinum, and 110ld . As a result of the relatively smaU size, heavy
nuclei. and tightly held electrons of their a toms. the elements in this series are also the
densest elements !do. = 22.61 g cm- J: d 1, "" 22.65 g cm- 3) .
Although in many respects relativistic effects nnd the lanthanide contraction serve
to make Ihe postlanthnnide elements less reactive than would otherwise be the case, in
other respects their bonding ability is increased. For example, bi.s(phosphine)plntinum(O) complexes react with molecular hydrogen. but the analogous palladium complexes do not :l
R 1P
Pt + H : -
R3 P
R3P
\I
M
/\
R,P
Rl
- X- H. +
H
Pd
(14.2)
R3P
Comparisons of gold and silver run her illustrate the point. The Au- H bond is much
stronger than the Ag-H bond and Au I; is much more stable than Agli. The
relat.ively high effective nuclear charge leads to relativistic stabilization (contraction)
of 6.r orbitals and destabilization (expansion) of Sd orbitals. The net result is greater
participation in M- L bending by the 5d orbitals and thus stronger bonds.
J Low. J. L ; Goddard, W. A., Ill

19116, j,
Schwcrdlrcg<1'. P.: Boyd, P. D. W.; Bum:l, A. K.; Robinton. W. T. ; Tuylor, M. J. lnorr. Owm.
1990.19, JS9}-l607.
580
14 Some Descriptive O.emistry of the Metols
Table 14.2
Some oxidation stoles of the m.tals of the first transition series
Gn>up
-=v-
OlOclotioto
1118
IVB
VB
VIB
VIIB
(3)
(4}
(5}
(6}
(7)
+1
+6
+.5
+4
+3
+2
+I
6
-1
-2
[VOJ'[VOFJ 2 [V(H20)6J3+
[V(H.z0)6]2+
[V(bpy),)+
V(bpy),
na.
[TI(H20)6J 3 +
-3
.:..4
The..!!
TJ(bpy),
[TI(bpy):,) [TI(C0)6J 2-
V(bpyJ,r
[V(CO),J3-
Various Oxidation
States of
Transition Metals
Low ond Negative
Oxidation States
[Cr(H.z0)6J2+
Cr(bpy),
[Cr(bpy),J(Cr(CO),J 2(Cr(bpy):J'(Cr(CO)J4 -
in two. Wid aso. and the + 7 oxidation stale is fouad in their anions. [Ruo.r and (OsO.r.
S(llle
Chemistry of the
[Cr0J2[CrOJ3 [CrOJ-
The entire question of oxidation state' is an arbitrary one and the assignment of
appropriate oxidation states is often merely a matter of convenience (or inconvenience!). The concept of oxidation stale is best defined in compounds between
elements of considerably different eleclronegativity in which the resulting molecular
orbitals are clearly more closely related to the atomic orbitals of one atom than
another. In those cases in which the differences in electronegativity are small and
especially those in which there are extensive delocalized molecular orbitals that are
nonbonding, weakly bonding, or antibonding, the situation becomes difficult. The
former situation is found with complexes containing halogen. oxygen. or nitrogen
cr-bonding ligands. The latter condition is common among organometallic complexes
for which often no attempt is made to assign oxidation states. ligands stabilizing low
(if imprecise) oxidation slates are cyanide and phosphorus triHuoride. both excellent
'ITbonding ligands. Hence it is possible to prepare zero-valent nickel complexes with
these ligands:
Ni(C0)4
+ 4PF3
---+
Ni(PF,)4
+ 4CO
K 4 [Ni(CN)4 ]
(14.3)
(14.4)
Ligands with extensively delocalized molecular orbitals that are essentially nonbonding can make the assignment of precise oxidation stales difficult or impossible.
For example. we have already seen this in the thiolene-thiolate ligands (see Chapter 12). A similar ligand is bipyridine, which forms complexes that may formally be
classified as containing + I, 0, or even - I oxidation states for the metal. A substantial
portion of the electron density on the metal in these low oxidation states is de localized
over the ligand '" system. Other instances of extensive delocalization stabilizing
For a book devoled entirely to lhe problems rdntcd to definina oxidation slaleS. sec
OnJntion Nu,U,.,n ant! Oxlclation Statr; Springer: New Yodt, 1969.
C. K.
Chemistry of the Various Oxidotlon States of Tronsitian Metals
....
581
Group
VIIIB
(9)
(8)
IB
liB
(10)
(11)
(12)
[NiFJ 2[NiFJ,_
[Ni(H,O)J 2
Ni(PPII,),Br
Ni(bpy)z .
(CuFJ 2(CuFJ 3[Cu(H20%l 2+

(Cu(CNJ2r
[Fe0J2 -
(FcOJ,_
[Fe04
[Fe(H20)Jl+
(Fe(H20)611 +
[Fe(NO)(HlOJ,Jl+
Fe(bpy),
(Fe{bpy)J[Fe(CO)J 2-
t-
[Co(l-norbomyi)J+
(CoFJ 2(Co{CN)i(Co(H20 )Jl+
(Co(bpy),]+
Co(bpyJ,
(Co(CO)J-
(Zn(H20)Jl+
Znz02
Zn(bpy),
metals in low oxidat.ion states are often encountered in biologjall systems (see Chapter 19).
Range of
Oxidation States
Although the definition of low oxidation states is somewhat subjective, it is possible to

discuss the
of oxidation states exhibited by various metals. When the metals of
the first transition series arc elUUllined, the results shown in T:lblc 14.2 are found.
There is a general trend between a minimum number of oxidation states (one or two) at
each end of the series (Sc,. and znH) to a maximum number in the middle (manganese, - 3 to + 7). The pauc ity of oxidation states ot the extremes stems from either
too few electrons to lose or share (Sc, Ti) or too many d e lectrons (and hence fewer
open orbitals through which to share electrons with ligands) for high valency (Cu. Zn).
A second factor tending to reduce the stnbility or high oxidation states toward the end
of the transition series is the steady increase in effective atomic number . This acls to
decrease the energies of the d orbitals and draw them into the core or electrons not
readily available for bonding. Thus, early in the series it is difficult to form species that
do not utilize the d electrons: Scandium(! I) is virtually unknown and Ti( IV) is more
stable than Ti(lll), which is much more stable than Ti(ll). At the other extreme, the
only oxidation state for zinc is + 2 (nod electrons ore involved) and for nickel. Ni(ll)
is much more stable than Ni(lfl). As o result, maximum oxidation states of reasonable
stability occur equal in value to the sum of Ihe sand d electrons through manganese
[CrVIOJ1 - ,(MnVUOJ - ), followed by a ralher nbrupt decrease in
(Tivo2 ,
stability for higtler oxidation states, so that the typical species to follow arc Fe( II , Ill),
Co(ll , Ill), Ni(ll), Cu(l , II), Zn(ll).
Comparison of
Properties by
Oxidation State
There are eert.ain resemblances amona metal ions that can be discussed in terms or
oxidation state but which are relatively independent of electron configuration. They
relate principally to size and charge phenomena. For example. the ordinary alums,
KAI(S0JzI2H 20, are isomorphous with the chrome alums, K Cr(SOJz 12H20, and
mixed crystals or any composition between the two extremes may be prepared by
582
14 Some Descriptive Chemistry of the Metol.t
substiwtion ofcrl + for Al 3 + . In this case the two cations have the same charse and
similar radii (rAJ' = 67.5 pm; rc,J 1S.S pm). There ore also examples of resemblance between
(r = 71 pm), Mn2+ (r 80 pm), and Zn2+ (r = 74 pm),6
despite the fact that one has a noble gas configuration (,.Zp6) and the ot.h ers do not (ds
and dt0 ).7 The remarkable resemblances among the lanthanides bear witness to the
overwhelming influence of identical charse and simi lar siz.e in these species. Likenesses that depend more on charge than on electron configuration might be termed
physical. They relate to crystal structure and hence to solubilities and tendencies to
precipitate. Coprecipitation is often more closely related co oxidati<Jn state than to
family relationships. Thus carriers for radioactive tracers need not be of the same
chemical family as the radioisotope. Technetium(Vll) may be carried not only by
perrhenate but also by perchlorate, periodate, and tctraftuoroborate. Lend(ll) has the
same solubility characteristics as the heavier alkaline earth mel:lls. Thallium()) (r =
164 pm) often resembles potassium i<Jn (r lSI pm), especially in associati<Jn with
oxygen and other hi&hly electronegative elements. Thus, like K , Tl + forms a soluble
nitrate, carbonate. phosphate, sulfate, and nuoride. Thallium(l ) CU1 also be incorporuted into many potassium enzymes and is exceedingly poisonous. Of course, some
propenies of cations (especially polnriz.ation of ani<Jns) are affected by elecU'Onic
structure (see Olapter 4). Thus we should not be surprised that with respect to the
heavier haJosens, n resembles Ag+ more closely than it does K+.
anot.h er chemical property that depends on the cationic charge is the
coordination number . Although it is greatly inftuenced by siz.e (Olnpter 4), there is a
tendency for cations with larger charges to have larger coordination numbers, e .g..
Co2+ (C.N.
4 and 6) versus cci' (C.N . 6), MnH (C .N.
4 in [MnCIJ2 - )
Mn4 + (C. N . = 6 in [MnFJ1 - ) . This is n consequence of the clectroneutrality
principle csee Chapter II). On the other hand, metals in extremely hiGh oxidation
states (Cr'{VI), Mn(VII), Os(VIII)) have n tendency to form metak>X}'I;en double
bonds (considerable ,. bonding from the oxygen to the metal), and four-coordinate
tetrahcdrnl species ([CrOJ 1 - , [MnOJ -, OsO.> result.
The Chemistry
of Elements
Po tassium-Zinc:
Comparison
by Electron
Although there are resemblances that depend only on the charge or oxid:1Ci<Jn state.
trunsition metal chemistry is more often governed by the electron configurati<Jns orthc
me tal ions. Thus, despite a nutural tendency for lower oxidation states to be reducing
in ch:1roctcr anti higher ones to be oxidizing, the electron conligur.stion may well make
the divalent, trivalent, or even higher oxidation states the most stable fo r a
metal. In this section the properties of the metals of the first transiti<Jn series nrc
briefly examined in terms of electron
Configuration
6 n.e similarity of abe nomcs of mqnesium and manpncsc: rcsubs from lhe confusion of these two
by utly chemises. an cm>r which has pcnisted amot11
chanislS 10 this day. Both
nounes derive uhimaldy from
an ancio:n1 city in
Minor.
7
Mi 10 the
No1<: tb:d Mc1 most closely resanbles Zt? and hiah lt>in Mn2 . The nscmblanc.c of
01hcr + 2 transilion melal ations is less becaute of LFSEs in complu.es oflhe toller.
II i.< ol\cn hclpfutto view the descriptive chemistry of1he 1ransilion mc.taiS from dill'emlt pct'Sf>CCIhu in a
SIIJdy. For a lhon>ttih review olaronsilion meJDI cherris1ry in an cl<mcnl-br
clement approxb. sec Ceo ton. F. A.: Wilkinson. G.
I1HJ111<1nh Clwmistr:-. 5th cd.; Wiley:
New Yorlt. t988. or G""'nwood, N. N.; Eatnshaw. A.
of /lor Elrmrnts; Pttpnoo:
Oxford. t9114.
lite Chemiotry of Elem..,ts Potassiu-linc
ThetJG
Configuratio n
The c/1
Configuration
This configuration occurs for sjmple ions such as K , Cal+, and g2+ and for the
formal oxidation states equal to the group numbers for many of the transjtion metals.
This holds tnJe as far as Mn(VII) (Fe(VIJI) is unknown).
All metal ions with d 0 configurations are hard acids and prefer to interact with
hard bases such as oxide, hydroxide, or
Complexation chemistry is less
extensive than for other configurations, but work in this area continues to expand.
lllere is no tendency for metols with this configuration to behave as reducing agents
(there arc no electrons to lose) and little tendency for them to behave as oxidizing
agents until spccie.s such as (Cr04 f -, (CrO,cl]-. Cr02Cl2 , and (MnOJ- are
reached. In general, therefore, their aqueous chemistry may be described simply: The
lower charged species cK +.Co2 +, ScH) behave as simple, uncomplexed (other than
solution.ocomplcx ions of scandium,
by water) free ions in
and [Sc(OH),JJ - , arc known and result when excess F- or OH- is added to insoluble
ScF1 or Sc(OH)J. The "crown" complexes of the alkali metals have been discussed
previously CCh:lptcr 1:!). and Co2 may be complexed by polydentale ligands such as
cdta.u The higher oxidation states [Cr(VII. Mn(Vll)) Lend to form oxyanions. which
are good oxidizing agents. especially in acidic solution: the oxides of the intermediate
species arc insoluble ITiO..I or amphoteric CV.Ot (V04]l - ) .
A quick survey of the metals with the d configuration yields the
descriptive information. For potassium, calcium, and scandium it is the only slllbk
clec1ron configuration. It is by far the most stable for ti&anium (e.g., Ti01 , lict4 ,
(TiFJ1 - ) . Vunadium(Vl occurs in the v::mall:uc ion, (V04 J' -, und a variety of pclyv:.nadates. It is a mild oxidizing agent givin& way to vanadium( IV) as the most stable
oxid:uion stale.'! The strongly oxidizing species (HCrO.r 1'1 to Cr,. 1.37 V) and
[MnO.J - tE' to Mn: is I.S I V) ore unstuble relottive 10 lower oxidation states.
This
not lend to be :1 stable configuration. It is comple tely unknown for scandium

in Til Ill). The later members of the series tend 10 disproportiona te to more stable
and strongly
+ 4Hz0
(14.5)
+ MnO: + 2H 1 0
(14.6)
3(Cr0_.) 3 - + l OW ---+ 2 (HCrO.r +

J(Mno.r -
+ 4H -
2 (Mno.r
T il.: only J <pccic< of impmmncc is the

form of vumtdium in aqueous 5olution.
The c/2
Configuration
S83
ion.
vO: . whit:h is the most stable
T his configuration ranges from Ti(lll. very strongly reducing, to FeCV U, very strongly
oxidizing. It is not a particularly stable configuration. BOih Ti(ll) and V( ll() arc
reducing agents and Crt IV) :tnd MnCV) are relatively unimportant . The ferrate(VI) ion,
if hard tia;>n.l<:>re absc:ntiFtywk. M. D. : Haddad,

D. J. CtH><d. Cl.rlfl. Rr. 1990. 911. tl7-2t11.
H)'llrolysis of Sc) is <,.lcn.o,ivc in
""'ucion tliCc Rrown, P. L.:
J.: S)'lv:l, R. N. J.
Cilrlff. Soc. Dullntt Trans. tWil, lS-Ill.
" Sec Sdllriclbaur. H.:
H. G.: Hq, J .
Ed. n6/. 1990, 19.
(or hiolotlicaJiy impon:.nl complexes or alk:olinc c:uth and :>lk:lli metoll ions. Coonlin.uion chctnislry
c:orth ions;. .olKO diS<:U><O<d in Poonia. N . S.: R;Voj, A. V. Clrrm. Rrv.
ofolkali melal nn.J
Soil bases will form c nmpk:Ac ift
T. S.:
tm . 79. Jl!9-441.
t! See CNpter t6 :11M! Fe. t6.9 for a ful discussion of the oxyanions or
-ium.
5 86
14 Some DltSCriplive Chemistry of the Metola
Fig. 1.1 Molecolnr

structure of diioclobia(o-
arsinellnickel(ll).
the octahedral complexes. If there is sufficient dispruity between the positions in the
spectrochemical series of L ond L' [e.g. diiodobis(diars)nickel(ll) , Fig. 14. 1]. the
resulting adduct is diamagnetic. The complex may be viewed os a square planar
complex that hos not been sufficiently perturbed by the tetragonal field produced by
the weak iodo ligands to cause unpniring of the electrons.
Only a few simple copper0U) salts. e.g.. KCuO:! ond Cs,CuF6 are known. but
num.:rous complexes containing organic ligands exist. These behave as might be
expected from their nnaJogy to Ni(ll), forming square planar structures. However.
unlike Ni(IJ), nil purely inorganic Cu( lll) species are strong oxidizing agents. Rela
tively stable CU(IU) complexes have been found in biological systems.
A few Co(l) complexes are known. nnd although IIley must be considered exceptional . vitamin Btz depends on this oxidation state for its action (Chapter 19).
The d 9
Config ura tion
The d10
Config uration
This configuration is found in copperlJI) compounds but is otherwise unimponant. It

has
t he closed subshell stability of d 10 nor tile LFSE possible
Co!>per1111 mny be fairly easily reduced to copperll) (see Eqs. 14. 10 ano.J 14. 111.
Six-coordinate complexes are expected to be distorted from pure octahedral
symmetry by the Jahn-Teller effect ond this distortion is generally observed (Cha!>'
ter l i t. A numberoflive-coordirote complexes are known. both square pyramidal and
lriconal bipyramidal. Four-coordination is exemplified by square planar and
tetrahedral species as well as intermediate configurations.
For the first transition series this configuration is lim ited to Cull ) amJ Zn!lll. 1>111 it is
aho exhibited by the posttr..msition metals in their highest oxillalion slates (Gal li II.
Get IV)). The copper( I) co mplexes arc good reducing agents, being oxilliz.al to Cu(lll.
They may be stabilized by precipitation with appropriate counlerions to the extcnl
that Cu(l) may form to t he exclusion or Cu( ll):
Cu2+(aq) + 2r(aq) Cul+(aq) + 2CN-(aq) -
Cul(s) + i l 2(s)
(14.10)
CuCN(s) + i(CN)z(g)
(14. 11)
Zinc( II ). gnllium(lll). and germanium(IV) are lhe most stable oxidation states for
these elements. but the later nonmetals (arsenic, selenium, and bromine) show a
reluctance to assume their highest possible oxidation slate.
1be spherically symmetric d 10 configuration affords no LFSE. so the preferred
coordination is determined by other factors. For Cu(J) the preferred coordination
appears to be linear (sp), two<oordinntion. nlthough tllree-coordin::ue complexes are
known as weD as several tetrahedral complexes. Zinc(II) is typicaUy either tetrahedral
(e.g.. [ZnaJZ-) or octahedral (e.g..
), but both l.ligonal bipyramidal and
The Ch..,istry of the Heo.;er Transition Metals
sa;
square pyramidal live-coordinate complexes are known (see Chapter 12). The posttransition metals form tetrahedral (e.g., [GaCI4r) and octahedral (e.g., (Ge(IICIICI,}+,
and [AsFJ-) complexes.
The Chemistry of
the Heavier
Transition Me tals
A detailed account o f the descriptive chemistry of the heavier transition metals is

beyond the scope of this book. Many aspects of the chemistry of these elements such
as metal-metal multiple bonds, met al clusters, organometallic chemistry, and coordination chemistry are discussed in other chapters . The present discussion will be
limited to a comparison o f the similarities aJld differences of the heavier metals and
their lighter congeners.
In general, lhe coordination numbers of the elements of the second and third
transition series tend to be greater than for the first series because the ionic radii are
larger by about 1.5-20 pm (O.IS-0.20 A> for corresponding species.w Thus tetrahedral
coordination is considerably less frequent althou&h observed in species such as
(WOJ2 - , [ReO.J-, and OsO Square planar coordination is found in tl' species such
as Rh(l), Pd(ll), Pt(ll). and Au(lll). which are especially stabilized by LFSE. Octahedral species are quite common, and the occurrence of coordination numbers 7. 8.
9. and 10 is fairly common.
111e heavier congeners show a pronounced tendency toward higher oxidation
states. Whcf'eas the+ 2 Slllte is known for nil elements of the first transition series. it is
relatively Wlimportant for lhe heavier metals. Cadmium is neatly restricted to the +2
oxidation state (Cd
is known21) :10d Hg(ll). Ptl(ll). and PIC II) arc the only other
important dipositive species. Although cobalt is known :1s both Co((l) nnd Co(Ill), its
congeners rhodium and iridium arc essentitllly limited to the + 3 oxidation st:ue or
higher. Chromium(lll) is the most stable oxidation state of chromium. but both
molybdenum and JUngslen are strongly reducing in that oxida tion stale with the + 6
oxidntion state being much more impormnt . In general. the stability of the highest
possible oxidation state (i.e . lhe group number oxidntion $t:llel is consider:lhly
greater in the he:wier metals. Thus [ReO.J-. unlike (Mno.J - , is not :t strOn(:oxidizing
age nt. The trend is extended fun her along the series M well. culminating in ruthenium
tetn.>xiJe anJ O$mium h:troxidc (both powerful oxidantsI . two of the few known cases
of v;d itl +II oxidation states .:: Fun her .:xnmplc:s :Ire the slahilitics of Pd( IV\. l'tUVI.
even ;1ble to achieve the
anti Aut II() relative to their li{:htcr congeners. Gold
unexpected oxidation stale of + S (see Chupter 18).
As Jiscus.'ICCI in Chapter II. there is t1 much greater tendency toward spin pairing
in the heavier transition metals and consequently the existence of high spin complexes
is much less common than among the earlier metals. Thus. in contmsl to Ni(ll), which
forms tetrahedral. square pla nar, !14juarc pyramidal. trigontll bipyramidal. and octahedral complexes, Pel( Ill and PI! II) form complexes Ihal nrc :>lmost universally low
spin and square planar. A few weakly bonded five-coordinate adducts a re known and
""
in cocrdi-iOII ""mber ....S in spin "otc comp&icwc direct comp;srison. The above
ranscw:>s Ulkcn from compori$on .:I
ond y l
IS prn lO.IS ;\)(. andZnH
and c:.f 1-lr
Bccausc:
""'' lw>idc conlr.letion. thc r.ldii cCthc third ..nes
are very simibr 10 tho<c of lhc sccon<l series. See pa,c 579.
: o Fqgjani. R.: Cillcspe. R. J.: Vcltris. J. E. J . Cllt"' StJ<'. Chrm.

+ 8 oxidalicln Slalc also is found in the amine campl..cs or
S . F.; Behrman. E. J. lnorz. Cloim. Mtu 198'7. 1!8, 21- :!6.
12 The
Co,.HoNif.
19116. SI7-S I8.
o.-o. <e.a OsO.pyt. Sec Kobs,
$88
s- Descriptive Chemiotry of the Metols

often appear as intermediates in substitution reactions of square planar complexes
(see Chapter 13). More recently it has been shown that this geometry c:1n be stabiliz.ed
with a ligand combination of chelating amines and '"accepting
The effect of
ligand field strength on the instability of the d9 configuration in silver{ II) and gold( II) is
pronounced. The splitting of the Sd ortitals in a d 9 Au( II) complex, for example, is
about 80"/. greater than that found in annlogous Cu(ll) complexes (see Chapter II).
The ninth electron of the gold complex would have to reside in the highly unfavorable
d,r-,1- orbital and this would lead to an extreme tetragonal distortion. Thus the odd
electron of Au(ll) is easily ionized and disproportionation to Au(l) and Au(lll) results.
There is also an important difference displayed by heavier transition metals in
their magnetic properties. Because of extensive spin-orbit coupling, the spin-only
approximation (Olapter 11) is no longer valid. 1llc simple interpretation of magnetic
moment in terms of the number of unpaired electrons cannot be extended from the
elements of the first transition series to their heavier congeners.
Finally, the heavier posttransition metals have aroup number oxidation states
corresponding to d 10 configurations: indium(lll), thallium( Ill), tin(IV), lead(IV), antimony(V), bismuth(V), etc. However, there is an increasing tendency, termed the
..inert pair effect," for the metals to employ p electrons only and thus to exhibit
oxidation states two less than those given above (see Chapter 18).
Oxidation States
and EMFs of
Groups 1- 12
Having compared in general terms the propet1ies of transition metals both on the basis
of the d-electron configura.t ion and the properties of t.h e ligtlt versus heavier metals,
we shaD now look more specifically at the stabilities of the various oxidation states of
each element in aqueous solution. Every oxidation state will not be examined in detail,
but the emf data to make such an evaluation will be presented in the form of a Latimer
diagram.
If you are not thoroughly familiar with the principles of dectrochemistry, you
should review Chapter 10 and the Latimer diagram derived there (below) before
considering the following discussion for determining the stability of oxidation states:
.u.
MnO; ...,. HMnO; u.oo Mn0 2 .!.!!12..., Mn1
l:ro
Mol' -=!1.4 Mn
A table of emf values appears in Appendix F.
Stabilities of
O xidation States
There are three sources of thermodynamic instability for a particular oxidation state of
an element in aqueous solution: ( 1) The element may reduce the hydrogen in water or
hydronium ions; (2) it may oxidize the oxygen in water or hydroxide ions; or (3) it may
disproportionate.
The emf values for reduction of hydrogen in water are given in Eqs. 10. 116 to
10. 118. These determine the minimum oxidation emfs necessary for a species to effect
ZJ
Albino. V. Ci.;
.St7-.S2S.
Jlnaa. D.;
De Fdicc. V.; Panunzi. A.;
A. Qrgolft}(MIDl/lc. 1917. 6
Olidotian Stoles ond f MFs of Groups 1- 12
589
red\Jction of hydrogen: I M acid, JtJ > 0.000 V; neutral solution, E > +0.414 V; I M
base, JtJ > +0.828 V. For manganese the only oxidation state that is unstable in this
way is Mn(O), which readily reacts with acid:
+ 2e-
Mn(s) -
+ 2e-
2H+(aq)
- + H2(g)
JtJ '"" + 1.18 v

JtJ
0.00 v
(14.13)
+ 1.18 v
(14.14)
JtJ =
(14.12)
The emf values for oxidation of the oxygen in water are given in Eqs. 10. 119 to
10.121. These determine the minimum reduction emf necessary fora species to effect
oxidat.ion of the oxygen: I M acid. 0 > + 1.229 V; neutral solution, E > +0.81S V;
I M base. JtJ > +0.401 V. There are several oxidation states of manganese that are
reduced by water. but the protonated manganate ion is typical:
HMn04(aq) + 3H+(aq)
2e- - + Mn02(s) + 2Hp

H2 0 -
!02 (g) + 2H+(aq) + 2e-
+2.09
(14.15)
JtJ
= - 1.23
(14.16)
E0
+0.86 V (14.17)
Species that reduce or oxidize water i:an be spotted rapidly in emf diagrams such
as the one given above for manganese. For example , in acid solution all negative emfs
result in reduction of H+ ion by the species to the right of that emf value.z All values
more positive than + 1.23 V result in oxidation of water by the species to the iefi of
that value. Examination of the manganese diagram for acid solution reveals that the
following species are unstable: Mn (oxidized to Mn2+), MnH (reduced to Mn2 +),
and Mn04 (reduced to Mn02 ). One should also examine the skip-step emf values for
possible reactions leading to instability. Thus, although water will not reduce Mn04
to HMn04. the skip-step emf for MnO; to Mn02 ( + 1.70 V) is sufficiently large to
make the reaction proceed:
2Mn04(aq) + 2H+(aq)
+ 2e-
H2 0 2Mn04(aq) + H20 2Mn04(aq) + SH +(aq) + 6e- - +
2HMn04(aq)
+0.90
- 1.23
v
v
(J4.J8)
!02Cg) + 2H+(aq) + 2e-
- 0.33
(14.20)
2HMnO;(aq) + l02(g)
Eo=
+ 4H2 0
3H 20 ___. i02(g) + 6H +(aq) + 6e2MnO;(aq)
24
2W(aq) __. 2Mn0z(s) +
0=
i02(8) + H 20
(14.19)
1.70 v (14.21)
Eo= -1.23 v (14.22)

Eo= +0.47 v (14.23)
Predictions based on cml Vllltocs are not aJWIIys borne our in the labor.Uory. FO<' example, pure
Mn(s) wculd be prediacd to react with neutral water but no reaction is obser<ed. In same cases
rca<:tions arc extremely slow and arc not observed
kinclic: rcssons. In others. prodUCIS or the
reaction, such as oxide eoalif11s, prOkct the rcaaant surfaces. Furthcnnore, reactions are usually
no1 run at standard conditions and then" values do not reflect the true spontoncity or the reaction.
ror
590
14 s - Descriptive Chemistry althe Metals
Oisproportionation occurs when a species is bolh a good reducing agent and a

good oxidizing agent. In basic solution. for example. Cl2 disproportionates to Cl - and
Clo- ions:
iCI 2(g)
+ e-
eo -
---+ Cr(aq)
iC1 2(g) + 20H-(aq) ---+ CIO-(aq) + H 20 + e-
+ t.4o v
(14.24>
(14.25)
= -0.89
!1 =
+O.SI V (14.26)
Species susceptible to disproportionation are readily picked out from an emf diagram
such as that given for manganese. The ' 'normal'' behavior of an element (i.e. when
uncomplicated by disproportionation) is for the emf values to decrease steadily from
left to right. Good reducing agents are on the right. good oxidizing agents are on the
left, and stable species are toward the middle. Whenever this gradual change from
more positive to more negative is broken, disproportionation can occur. For man
ganese in acid solution such breaks oocur at two species: Mn)+ and HMnO;. As it
turns out. both ions are also unstable because they are reduced by water, but even if
they were stable in this regard they woold be unstable as a result of disproportionation
reactions:
Mn)(aq)
Mn 3 .. (aq)
+ e-
0 =
---+ MnZ+(aq)
Mn02(s)
+ e-
I.S6
v.
(14.27)
E0 = -0.90 V (14.28)
eo =
+0.66
(14 ..29>
Other applications of emfs include the prediction of thermodynamically possible

redox reactions (e.g . will snoxidile FeZ+ to FeH?) and the stabilil3tion of oxidation stales through the formation of complexes. The former is a straightforward
application of thermodynamics and will not be discussed further here . The second is of
great importance. It was introduced in Chapter II and will be discussed further below.
The EHect of
Concentration
on Stability
The Nemst equation was given before (Eq. IO.I IS). and in this chapter the effect of pH
on the reduction potential of the hydrogen ion has been mentioned, but the effect in
gencml should be emphasized. There are several types of reactions in which con
centrations of the reactants and products affect the stability of various oxidation
slates. This can be understood through application of the Nemst equation. The
reduction potential of hydrogen will vary with the concentration of the hydrogen ion;
hence the commonly known fact that many reasonably active metals dissolve in acid
but not in base.
Perhaps even more important is the effect of hydrogen ion concentration on the
emf of a half-reaction of a particular species. Consider the permanganate ion as an
oxidizing agent in acid solution (as it often is). From the Latimer diagram above we
can readily see that the reduction emf is l.S I V when all species have unit activity.
What is not shown is the complete equation:
(14.30)
which makes il clear that the concentration of the hydrogen ion enters the Nemst
equation to the eWllh power- the oxidiling power of the permanganate ion is strongly
pH dependent. If the hydroge.n ion concentration is reduced to 10- w M (I M OH-l. a

is obtained:
different set of
Thus there are oxidation states o f manganese that are unstable in acid buc smble in 1 M
base. In the above discussion we have seen that the tendency for a species to accept or
provide electrons. as quantified by emf values, may be strongly dependent on pH. Our
examina tion has been restricted to aqueous solu tions of MnO; in which the pH is
either 0 or 14. A fuller picture of the equilibrium chemistry of manganese. showing a
broad range or pH and E values, is given by a Pourbaix diagram (sometimes called a
predominance area diqram) (Fig. 14.2). 25
o f this type are temperature and
concentration specific; in this case concentrations are 1.0 M for all species but H. and
OH- and the temperature is 2S c.:!6 Dolled lines representing !he oxidation and
reduction of water have been added. Any species above or below these dolled lines
will . in p rinciple, oxidize or reduce water, respectively. In practice the range of
sl:lbility in water is larger than that depicted because of
It is instructive to examine
14.2 in some detail. In this diqram we see
horizontal. slanted. and vertical lines. The solid lines wise from values of :lnd pH at
which two different oxidation states can exist in equ ilibrium. T he equat ion for each
sulid line is given by;
u _ (0.0592)(m)(pH)
n
(14.31)
where n is the number of electrons required to reduce the higher oxi.J:uion st:lle
m
is the number or hydrogen ions consumed. For example. a t all points on solid line A.
an equilibrium exists between Mn(s) and
The line is horizontal because
there is no pH dependence for the reduction:
Mn 2 (aq)
+ :ze
Mo(s)
(14.32)
At some higher p H, MniOH l2(s) becomes the predominant species :toll us is shown by
solid line D. the voltage varies with pH. consistent with the half-reaction:
Mo(OH).(s)
+ 2e -
__..... Mo(s)
+ 20W(aq)
(14.33)
The vertical
line C shows the p H a t which Mn:caq) 11nd MnCOHl.(s) exist in
equilibrium at unit activity:
(14.34)
This, of course, is an equilibrium between two species of lhe same oxidmion state and
therefore does not involve oxidation or reduction.
"Can-..,b:U. J. A.: Whitclccr. R. A. J . CM1t1. Edtor. 1969. 46. 90-92. J>ouri)ax. M. AtltU t1/ a ...
trocMmiNJI Eqrdlibr/tJ In AyomJUI Sol11tlntr
tronslntiun by Fr:>nklin. J. A.l
Ql(fonl. 1966.
C. C. In Eneyc/tJpN/ia of Eln-trtKNtlli>lry of IM
Bard. A. J Ed.;
llbn:d Dcltker: New Yoolt. t973.
u.na.
"" Gedosisl5 ollen construct their PO<IIbaix

mo<"C c:losdy to tlw rOUIICI in IIA!d"e.
based "" vuy dilute ...Uicns 10 caTCSj)lliiCI
592
U Soo,.. Descriplive Ch.....ntry of the Metals
Fig. 14.2 A pOieniWpH

(Pourbaix) diasram ror
mansanese. (Modified from
C. C. Liana In EncyclopeJia of E!tctrochtmislry
of the Elements; Bard.
A. J . Ed.; Marcel
Dckku: New Yock, 1973;
p 360. Reproduced with
pcnnission.l
+0.4
>
-o.s
-1.2
- 1.6 0
pH
Species existing at high-voliages (e.g., MnO;) are good oxidizing agents while
those at low voltages (metallic manganese) are good reducing agents. II is clear from
Fig. 14.2 that manganese in the + 2 oxidation state is the predominant species over a
wide area of pH and potential combinations. The half-filled d shell for Mn2 is thought
to be largely responsible for this stability.
Manganese(lll) oxide, Mnz01 (s). exists in equilibrium with Mn(OH)::(s) (line 0) if
conditions are sufficiently basic or with Mn1 +(aq) Cline E) al somewhat lower pH
values:
M o 20,(s) + J H 20
+ 2e- - - + 2 Mo{OHh(s) + 20H-(aq)

Mo 2 0 3 (s) + 6H+(aq) + 2e- - - + 2Mo2+(aq) + 3H20
(14.35)
(14.36)
Mn2 +(aq) (acidic conditions) and
Lines G and F show equilibria between Mn02(s) and

between
and Mn20,(s) (more basic conditions), respectively:
MoOis) + 4H+(aq) + 2e- - - + Mo2+(aq) + 2H 20
2Mo0is) + H 20
+ 2e-
---+ MD203(s) + 20H- (aq)
(14..37)
(14.38)
Above line H the predominant species is MnO;(aq), while below line H Mn02(s) is
dominant. AI the far right side of the diagram, line H intersects with lines I and J,
creating a small triangle of stability for Mn<>!- (aq) and making it the predominant
species in that area.
Oxidotion Stotes oftd EMFs o f Groups 1- 12
593
It should be kept in mind that only species thal can exist in concentrations
corresponding to nn activity of one are shown on this particular diagram . For example,
the solubilities of Mn<OHh(s) and Mn20J(s) increase in strong base presumably due to
the formation of some Mn(OH)!-(aq) [or Mn(OH))J and Mn(OH>;. respectively. but
these anions are not shown in the diagram. The hypomanganate ion, MnQ!- (aq), has
been detected in basic solution, although not at concentrations approaching 1.0 M.
Known species, such as Mn(OH),(s) and Mn20 7 are absent because of their thermodynamic instability.n Some species are just outside the range depicted . For example, MnH becomes the predominant species in IS N Hz504 at a potential of I.S V.
Finally, some species such as Mnl04(s), have been omitted from the diagram in order
to minimize its complexity.
The subtlety of concentration effects may well be illustrated by the puzzlement
once occasioned by the inclusion of dry iGe in a list of ingredients for the preparation
of potassium permnnganotc-all the more so because it was obvious that the dry ice
was a true
not a coolant. Tile preparation takes advantage of the fact that the
oxidotion ernfs of manganese are more favorable in basic: than in acid solution: One
can oxidize the readily avail:lble manganese dioxide to the green manganate ion,
[MnOJ 2-, with an emf of only -0.60 V to overcome.
E' = -0.60 v (14.39)

Since this half reaction is so hi&hly hydrogen-ion sensitive, we can force the reaction
even more by increasing the hydroxide ion concentration above I M, say, by using
potassium hydroxide (for an example c:A a nonaqueous. fuscd-5alt reaction. see
Chapter 10). Now, how can we get mangan:lle oxidi:ted t.he remainder of the way to
perrnanganate? By increasing the hydrogen ion concentration and gradually shifting
over from the basic toward the acidic Latimer diagram. As shown by this diagram.
(Mn04] 1 - (aq) disproportionates in acidic solution, forming two moles of pcrmanganate for every one c:A manganese dioxide.
4H+(aq) + 3(Mn04 ) 2 -(aq)-----+ MoOJ(s) + 2(Mo04 ) - (aq) + 2H20
(14.40)
But how can this acidification be effected without adding large amounts of strong acid
(recall that permanganate is unstable in concentrated acid)? Simple; Dissolve the
potassium mnnganate/potassium hydroxide mixture in water, throw in a few chunks
of dry ice. and in the "witches' cauldron" effect. watch the solution tum from green 10
deep purple!
Group lA (1)
T hese active metals lose one electron readily, but the loss of a second is energetically
very unfavorable (see Chapter 4). Thus the chemistry of the group is nearly defined in
terms of the + I oxidation state. As these metals are powerful reducing agents. it is
understandable that the reduction of M+ is very unfavorable:
K (aq) + e- -
K(s)
- 2.94 V
(14.41)
The emf values for Li+, Na+, Rh+, and Cs+ are - 3.04, - 2.71. - 2.94, and -3.03 V,
respectively. Although lithium metal is the most easily oxidized in the thermodynamic
sense, it is less reactive in water than the other alkali metals because of its relatively
high melting point (180 "C). The others become molten from the heat of reaction,
mehing at less than 100 "C, and as a result expose a much gtentcr surface area.
17 Addifl&
.Ufuric ac:icl 10 cold
subslance, llra1 explodes Yiolclllly.
solutions Jive M
a Ira-ish oily
594
14 Some Descriplh Chemistry of the Motols
Alk:llitle anions. M-, discussed in Chapter 12. may be stabilized by various

macrocylic ligands.28 The dissolution of sodium and heavier alkali metals in ethers
gives not only solvated M+ and e-. but also solvated M-. which results from
disproportionation of the metal atom.29
(14.42)
Group IIA (2)
The relative ease with which both s electrons are lost from atoms of these elements
as
leads to compounds in which only the +2 oxidation state is found. In
discussed in Chapler 4, M+ is unstable with respect to disproportionation. The metals
of this group are less strongly reducing than the alkali metals. but still must be
considered strongly reducing.
Ca2 +(aq) + 2e- -
Ca(s)
E'"" -2.87 v
(14.43)
The emf values range from - l .tr/ V for Be to -2.91 V for Ba.
Group 1118 (3)
Scandium. yurium. and lanthanum are all quite active. resembling the alkaline earth
metals <IIA. 2) to a certain degree. For example. they reduce water. react with
oxygen. and dissolve in strong acids to give soluble salts. The + 3 oxidation stale is the
only important one for this group, and aqueous Ml+ cations have been extensively
studied. Scandium(lll). with its high charge and small radius, resembles AJ)+ in its
chemistry. The lanthanides will be discussed later in this chapter.
Sc3 (aq) + Je-
Group JVB (4)
---+
Sc(s)
f:'l = -209V
(1.$.44)
Titanium has a more extensive redox chemistry than either zirconium or hafnium. In
addition to the + 4oxidation state, the most stable for all three elements of this group.
titanium( Ill) and titanium(ll) compounds are known. Titanium( Ill) is a good reducing
agent and exists in aqueous solution as (Ti(H 20)J3+ under acidic conditions. Tr
tanium(IJ) reduces water. but in some instances the reaction appears to be sufficiently
slow to allow this oxidation state to be detected. Significant hydrolysis of the + 4
cations occurs, more so for the small titanium(IV) than for the other two members of
the group. Hydrolysis of Ti4 + leads to a mixture of species. including
'.
'.and various oligomers.w
--=-:!.< '-......Ti
Potentials in parentheses are estimated values.
Group VB (5)
A wide range of oxidation states are known for all of the e.lemcnts of this group, but
only vanadium has an extensive redox chemistry.
""D-Jwes. S . B.; Ellllboocly, A. S .; Dye. J . l.. I . Am.

Soc. t987. 109. 3SOII-3St3.
""Dye. J. L. Prog.
1984,12. 327-44t .
.>o Gr.ltzel. M.; Rotzins..-. F. P. /norg. Chtm. 198S, 24, 2:320-2321. Comba, P.; Metbach. A. lnorR.
Ch,m. t987, 26, 131S-IJ23.
OxidatioR States aRd EMFs at Groupo 1- 12
595
-on
- 0.611
Nb
Ta!0 1 - - - - -- ......::.!!o.>!i':......- - - - - --+ Tn
Oxidation states of vanadium are found as low liS - 3 nnd as high as + 5 (see
Table 14.2). Vanndium(ll) is strongly reducing nnc.l nlthough aqueous solutions of the
violet
ion can be prepared. they are inherently unstable with respect to
water reduction . Vam:WiumC III ). though st:lble in water, is a fairly strong reducing
as well. Vnnndium tV) a good oxidizing agent. but only in concenlr.ued acid.
The dependency on the
ion concentration is such lhat in neutral solutions
t he rco.luction potemial is lowered 10 such an extent that reduction of VCV) is difficult.
The + 4 oxidation stnte. which is generally Ihe m.ls l st;lble one for vanadium. is best
reprC$cnted by the vanadyl ion.
which is stable in aqueous solution and
has a rich isopolyundergoes complexruion with a wide r.1nge of ligllnds.
anion chemislry. wbich is discus'ed in Chapter 16.
1bc lower oxio.l:uion s1:11es of niobium and lanlalum are unimportanl compared lo
tlu: + S slate. Because of the ccncr.!l insolubilily of the oxides nnc.l 1he lnck of stable
lnwer oxio.lalio>n
there is lillie wlution redox chemislr)'. :-.liobiumtlll) does
appear to form upon the reduction of niobiumtVl with zinc . nno.l is stable in the cold in
the absence of air. btJt if the solution is hellled. decomposition .xcurs with precipitation of
oxides.
Group VIB (6)
Chromium continues the p:altcm we have seen for vnn01dium: The highest oxidation
stale is strongly oxidizing. the lower ones are stronsly reducinc. ano.l some intermediate states o.lisproportionnlc. Blue aqueous solutions of chromiumt lll can be prepared
by o.lissolutinn of pure metal in oxygen-free acio.l
or h) reduction of chromiumtlll). Thcc 'ulutions
and unsl:tblc with rcsrccl to wnter
reduction. The +
can be st:thili7.cd lhrnugh complexation or formannml>.:r uf com,.lunds is known ftlr chromium(lll), the
liun f insoluhl.: ' ails. 1\
most
furm fur this ek mo:m . Chromium( VI) is a powerfUl <lxidiz.ing
in acid
solution (<IS dichromate). but because <lf Ihe hydrogen iun Jependencc. it is much less
so in basic sllutiun (as chmmale).
-..:::;
0.':,!__,
Crz. -::
-.::"'::...'___, Cr
...... ""
t-f)JJI)
___...:.:::=:___ _ __, W0
- ..!:'""=.."-+w-o.o
S 96
14
So O.Scnptiv Chemistry of th M.tols

The heavier congeners, molybdenum and tungsten, have a less interesting redox
chemistry. The emfs are small and the differences relatively unimportant. The chemistry of these elements in iso- and heteropoly acids, multiple bonds, etc. is generally of
more interest (see Chapter 16).
G r oup VIIB (7)
Tile first member of this family, manganese. exhibits one of the most interesting redox
chemistries known; thus it has already been discussed in detail above. Technetium
exhibits the expected oxidation states, and associated with these ure modest emf
values. All of the isotopes of technetium are radioactive but 99 Tc has a relatively long
half-life (2.14 x lOS years) and is found in nature in small amoums because of the
radioactive decay or uranium. Oxidation states of rhenium range from + 7 to -3, with
some species (e.g., Re03 and ReH) unstable with respect to disproportionation .
TeO;
..,0.4
......
ReO-
I+G.'7ZI
(8, 9, 10)
,_
Re03
Group VJIIB
(.0.11
Tc01
Tel+
I.a..
Tel
t-O.JJ
Re 3
....,.
Tc
+UI
Re02
r1
G..! I
<oG.JI
.o.2l
Re
Historically the triads of Fe, Ru, Os; Co, Rh. lr; and Ni. Pd. Pt huve been called
collectively Group VIII B. This heterogeneous assortment of elements was combined
into a single family more from a desire not to have any croup number exceed eight, a
"magic number" in chemistry even before Lewis formalized it in his octet theory,
than from any compelling logic. This. of course, ignored the fact that the set of five d
orbitals has a capacity of ten electrons, and thus there should be ten families of
transition elements. Although not fUlly agreed upon by all chemists, The Commission
on Nomenclature of Inorganic Chem istry (1990) has recommended that numbers 1- 18
be used instead of Roman numerals followed by A and B designations. Thus the three
triads now appear in separate groups (8, 9. and 10) and this perhaps is as it should be
since the chemistry o r iron is not more simil:1r to th:lt of nickel th:ln it is to that of
chromium.
I.OA
Ruo ..,.,.
II.A)
OsO
t +G.$1)
Ruo;..!!!:!!.....Ruo ---'-":.;;'"';.;'-- RuO ,....,,
...
.>)
0s03 .....!:!:!!..-. 0501 -l::!!!.... Osl+

IJIZ
TI
.o...,
Os
Oxidation Slole
CoO,
RhO,
$!1.1)
Rh02
,......, ocr
1.9'1
co:
-ou
RJt'
1.0.11
RJt;
O.
I+IJ'
lrO, -..or..,
IJ:.:...
I-
-+1
597
EMFs of Gt1141po 1-12
Co
Rh.
(+t,O)
J2.16
w, -..>:t;:oo,,._,,_
Rh
...,lr,.-- - "''"""9"-----oorr
'
1be pattern we have seen in the immediately preceding elements conlinues with
iron and its congeners-the metal and + 2 oxidation state are reducing, the higher
oxidation states are oxidiz.ing species. Members of the cobalt and nickel families,
however, tend to be Slable only in the + 2 Ollidation state unless stabilized by
complellaticn. The reader may readily apply the methods illuslnlted previously to
eltamine the relative stability of the individual oxidation states.
The Group VJIIB (8, 9, and 10) metals illustrate well the point made previously
that heavier congeners more readily assume higller oxidation states. Thus iron. cobalt,
and nickel ore effectively limited to + 2 and + 3 oxidation states. but oil of their
congeners have reasonably stable higher oxidation states.
Group 18 (11)
The elements copper. silver, and gold show such anomalies that there sometimes
appears to be lillie congruence as a family, with the member that is least reactive as a
metal (Au) being the only one that has an appreciable chemistry in the +3 oxidation
s tate and also the only one to reach the - I and + S oxidation states (CsAu and AuF5),
although both copper and silver may be ollidized to + 4. The members of the family
more or less routinely (silver less frequently) violate the very useful rule of thumb you
have seen eartier: The maximum oxidation state of an element is equal to or less than
its group number (IB, IVB, VIIB, etc.). Thus we have CuS04 , AgF1 , and [AuCIJ-.
Each member of the family has a different preferential oxidation state (CU. + 2; Ag,
+I; Au, + 3). 1be one property they do have in common is that none has a positive
emf for M --+ M"+ ; therefore, the free metals are not affected by simple acids, nor are
they readily oxidized otherwise, leading to their use in materials intended to last)l
Jl Copper and silvu will dssolve in nilrit ocid or hot au.uric add. A mixhn or
and
nitric acids (aqua rqial wiU dissolve IQkl. II has
"-> reported th:u mitura or haJosens
and quaJCrTillly ammoniun halides in orpnic solvenls dissolve aold rascer !han docs aqua rqia; sec
Nakao. Y. J. Clotm. Soc. Chmo. CommiUI.
426-417.
'"""'ty
598
14 Some D. .criptive Ch-istry of the Metols
This tOGether with their market vnlue, has led to the term coinage metals" for the
members of this family.n
Cul+
....!!.!.L.cu .....t.!!:!L.cu
C+I ..SO)
Although copper fonns compounds in any of four different oxidation states. only
the + 2 state enjoys much stability. The + 3 state is generally too strong an oxidizing
agent. though Cu(lll) has been found in biological systems. Complexation by peptides
can lower the reduction emf to the range 0 .4S-l.OS v .n The free + I ion will
spontaneously disproportionate ( +O.S2 V > + 0. 16 V). Copper( I) compounds are
known. however, in the form of complexes such as (Cu(CN>.r, [CuCI..r.
(CuCI,f .:u or as the sparingly soluble halides.
Silver forms stable compounds only in the + I oxidation state. all higher states
being strong oxidizing agents. Even silverW is not overly stable, as shown by the lar!;e
reduction potential (0.80 V), and has become a common oxidiz.ing all"nl in inorganic
and org:mometallic synthesis.)' The photosens itized reduction of silver
is. of
course. the basis of photography.
None of the oxidation states occurring in gold compounds can really be said to be
thermodynamically stable . Gold <Ill and gold( I) are subject to disproportionation. The
reduction potential of gold(ll l) to gold( I) is margjmlly above that necessary to oxidize
water . but the presence of complexing agents can stabilize + l and + 3. with the latter
usually being the more stable.
G roup liB (12)
The
configuration of this family is not conducive to an extensive redox chcm
the s
to form stable + .::uions;
istry. The overwhelming tendency is to
indeed. this essentially describes the entire redox chemistry of z.inc.
)!
These meW. occur in dcmcntary ronn in nature an.l...:re probably tho fint mctols k...,.....,. Gold
and oliver""' now comi<lcred leo voluable 10 usc in coins and hove been replaced by less cxpcn.'livc
metals. Alloys dc:ojlpa' (c.a. . the "nid.cl" coin i.s eotnroo<cd of7S% COpper and 2J% nickcllore
stia widely used.
D. W.: ()wefts, G. D. ln Mtml f o11u on BI<>IDttk al Systems; Siad. H . Ed.; l'obcl

Dekker: New Yorit. 1981: Vol. 12. p 7S.
K. L.: Grush. M. M.: K..u., K. S.
Chtm. 199t,l9. JISO-JISJ.
l>
S. for CJCillnjlk. Couon. F. A.; fef\1. X.; Mw-. M. 1""'11 Clonn. ' " ' 2ll. J9.1-MI.
T11e Lo,.tt.anide and Actinide EJ--t
QP
599
---+C<W
- 0,<10
- O.IJ
Hgl-----"""""'"-'----....
_ __..:.:O\lOO::.:;:::.._ _ Hg
The ability of mercury to form an Hg- Hgbond (cadmium to a much less extent)
plus a greater tendency 10 form coordination compounds compared to the mher
members of the group incrQseS Ihe complexity of ils U!timer d ingrnm somewhat. but
not much. Its electrochemistry is straightforward. with both mercurylll and mercury( ll) being stable in uqucous solution .
The Lanthanide ond

Actinide Elements
Stobie Oxidation
Stotes
This section inclulles the

of
elements 1...'1 10 Lu. and Ac to Lr."' In
addition. some specul;,tions al"( ma.Je concerning heavier clements th:ll m:lY be
synthesized in the future.
The JanlhanitJcs ;tre char:.cleriLaJ by sr...Jual filling of !he 4/ subshell and !he
actinides by fiUing of the 5)" suhshdl. Th.: relative
of tho: 111/ and (11 - llf
orbitals are very
:md
to the
lf
<>rbitals tfig. 14.3J.J7
The electron
of the neutr:ll atom' c.ce T :ct>le :!.II thu. shll"' some
irregularities. Noc able is che )table/- .:onligur.uion f<>nnd in Eu. Gd. Am ..md Cm. For
the + 3 .::ttions of both tho: lanthaniucs and a.:cinidl!s. however. there is strict regularity; all have 4j'Sd"6Jl or
cllnfigurntions.
In many
the .:h.:ncical
of the lanthanides are rerented by the
accinidcs. Much u-c of I sin1it:cri1y was m:o.le uurinll the early work on the chemistry
of the synthdic
Given th;u these dements were o n en handled m very small
quanliliCS and ;lf\! r.I.JionCi ii'C, l'f'!.lil:lkiO 11f their rrorcnie s by analosy h> the lttn
series proveu very hdpt'ul . Out he mh.:r han.J. it should Ol11 be lh,mghl that the
uctinidc series is merely a replay llf the lant lmnidcs.
lii'C
sij;nifkant
dincrcnces between
''"" serie s rcl:1tcu
tu the d illcrcnccs
the 4f
and Sf orbitals.
The characteristic oxidation state llf the l<cnthonidc clements is + 3. The universal
preference for this oxidulion stale tosether with the notable similaril y in size led to
grertl difficulties in tho: sepaMion or the..: elements prior 10 1he development of
"' Mmc cho:mis1. would .:on>klo:r lhe clc-m\:nc l.a

A.: lube ,., Gruup) ond nol l:lnth.,nioks or
HOWC'Yff. i1 has ho:cn
""
ctw La :1nd Ac :.men:
properly placed in the !"'rio<lic lab!< 8l< tho: liN l'l"'Cf'nbers fL lllc tiU>Ihanid<! ;1110! actiniok scric> 3J1C1
IMI Lu and IJarc: bc>t placed in Croup). ,S.,c
k n..:n. W. D. J . Chrm. &ltH". t911l.
.59. 634-636.
11
COfl'll"'l"' lllc
ul
Mrnilov problem cJ \'CnU s urt>il31>1 in Jr:>n>iiJC>n rn<:lab. Chapter 2.
600
14 Some Desaiplive O.emisWy of !fie Metals
40
30
EnclaY
20
10
.5
sc
- 10
- 20
- 30
- 40
nl
Ce
...
10 II 12 13
14
Nd Pm Sm Eu Cd lb Dy Ho t Tm Yb
Ac Th Pa U
Np Pu Am Cm Bk Cf Es Fm Mv No
ar;Jrs
Fig. 14.3 Approximate relative enerJies oither-'1d 1s 1

dectroo configurations.
[From Fred . M. In
CMmisuy; Fields, P. R.: Moeller, T .. Eds.;
Advances in Chemistry 71; American Chemical Society: Washington, DC, 1967. Reproduced
with permission.)
chromatographic methods.J8 Despite their propensity to form stable + 3 cations, the
lanthanides do not closely resemble transition metals such as chromium or cobalt. The
free lanthanide metals are more reactive and in this respect are more similar to the
alkali or alkaline eanh metals than to most of the transition metals . They all react with
water with evolution of hydrogen. One difference lies in the sum of the first three
ioniz.ation energies-from 3SOO to 4200 kJ mol- 1 (36 to 44 eV) for the lanthanides,
compared with S230 kJ mol- 1 (S4.2 eV) for cr>+ and 5640 kJ mol- 1 (S8.4 eV) for
Co3 .. . A second factor is the heat of atomization necessary to break up the metal
lattice: Transition metals with d electrons available for bonding are much harder and
have higher heats of atomization than the alkali, alkaline earth, and lanthanide metals.
Two lanthanides. europium and ytterbium, are particularly similar to the alkaline earth
clements. They have the lowest enthalpies of vaporiz.ation and the largest atomic radii
of the lanthanides (Fig. 14.4), making them more similar to barium in their properties
than to typical lanthanides. Presumably these elements donate only two electrons to
the bonding orbitals ("bands") in the metal and may be said to be in the "divalent"
state in the metal unlike their congeners. These same two elements resemble the
"' For a discussion of Ihe difficull;es and confusion surrounding the early chemislry of these elements.
see Systmttllits and
PropmlDo/tM
P., Ed.; Rcidel: Boston. 1983. and
Kremers. H. E. J.
Edut. 1915, 62, 665-667.
2JO
Fig. lU Atomlc nldii of

bari<Jm, lanthanum. lhe
lanthanides, and hafnium.
(From Spcddq, F. H.;

Daane, A. H. Tl"
&mlu; Wiley: New Yen,
1963. Reproduced with

pennission.J
!.i
11
"'
160
150
--
S6 S1 53 SP 60 61 62 6J 64 6S 66 67 68 69 70 71 72
alkaline earth metals in another respect-they dissolve in liquid ammonia to yield

conducting blue sOlutions (see Olapter 10).
Althouah + 3 is the most characteristic oxidation state of the lanthanides (the only
one found in nature), the + 2 oxidation state is of some importance.:w As might be
anticipated from the above discussion, Eul+ and YbH are the most stable dipositive
(from
species. 10ese ions are somewhat stabilized by 4/7 and 4/14
exchange energy) el1joying the special stability of halflilled and filled subshells.40
Aqueous solutions or Eul+ ,
and Sm:+ can be prepared, but all reduce water
over time (Ytr+ and sml+ rapidly) and all are readily oxidized by oxyeen. Other
lanthanides (Nd. Dy. Tm, Ho) form M(ll) compounds which are stable as solids
(Table 14.3). Not all "divalent" lanthanide compounds are truly such; i.e., some
do not contain M(ll) ions (see above). For example,
Cel2 , etc. have been
formulated as MJ+(I - )2e-. Although this formulation appears stran&e because
of the free electron, it is not more so than Nae- encountered in Chapter 10 or
{K(crown-6)J[e(solvent)] in Chapter 12. However, in contrast to the electrolytic be
havior of these elect rides in ammonia or crown ether solution, the lanthanide diiodides
have de localized electrons and are actually considered to be metallic phases.41
Oxidation states higher than + 3 are exhibited by Ce. Pr. and Tb. but only Ce4 is
stable (kinetically) in water. It is a very strong oxidizing agent in aqueous sokllion
(0
1.74 V) and is used as a vOlumetric standard in redox tilr81ions. Some or its
salts {e.g. cerium(IV) ammonium nitrate , cerium(IV) sulfate] lind application in
w,
)9 Johnson. D. A. A.dv. lnDrf. Clrtm.

93-107. Mikbcev. N. 8 .; Kamcnskaya.
lt77. 20, 1-1)2. Meyer, 0. Clwm. Rt<. 1988, U,
A. N. C()(Nd. Chtm. Rtv. 1991, 109, 1-S9.
""EJ<c:hange eneray ossocialed with nearly talf-lllled and filled conllaurotions of sanwium(ll) and
thulium( II) is not thoucht lo conlriboue much 10 the stability of halide saliS.
Jclu>Son, D. A.
J . Clwm. Educ. ' "' $1,
for thamod)'f*l'lic
Corbell. J. D. In Sq/id Sttu CMrnisrry: A. C<mltmpo<ary O..tr>Ww; Holt, S . L.; Milslein, J. 8.;
Robbins. M.. Eds.; Advances in Cbdnistty 186; American Cbcmial Sociely:
DC.
1*: Cbapter 18.
602
14 s...... Oescriptiwe Ch..,istry of the Metals
Tobie 14.3
OxHfolion stat.. ol
lanthanides and odinicles
Symbol
2+
3+
4+
Symbol
1+
2+
3+
4+
5+
6+
7+
La
Ce
+
+
+
(+)
Th
+
(+)
Pa
(+)
(+)
Np
Pu
+
(+)
(?)
Pr
Nd
(+)
Pm
Sm
Eu
Ac
+
+
+
+
+
t+)
Bk
Oy
(+)
(+)
cr
(+)
+
+
+
+
Ho
(+)
Es
(?)
+
+
Gd
Tb
Ec
Tm
(+)
Yb
Lu
+
+
+
+
(+)
Am
Cm
Fm
Md
No
Lr
(7)
(+)
(?)
(7)
+
(+)
(?)
(7)
Abbreviations: +. exists In solution: ( +), fou"" in solid Sllle only; (?). cklimed bul not
Bold fiiCe rep-uents the most stable oxidation stale. For lan.tlanidc:s, sec
Meyer, G.
1988. 88, 93-107. For -=tinides. see Katz, J. J .; MorM. L. R.; Snbor..
G. T. In Tltr Cltmoistry qftlrr AnilliJt EMtMnts; Katz. J. J., Seabo<.. G. T.; Morss. L. R.
Eds.; Chapman and Hall: Londnn, 1986: Vol. 2, Cllapttr 14.
organic chemistry as oxidizing agenls .z Although all or Jhe actinides exhibil a + 3

oxidalion slate. it is not the mOSI Slable one for several of them. Thorium(lll) und
procacliniumflll) exisl in lhe solid state only. and nhhough uranium{lll). nepluniurntllll. nnd plulonium(lll) have nn aqueous chemistry. sreuter st:1bili1y is found
in higher oxillalion states. In contrast to the lanthnnldes, the uctinitlcs
their f
ele.:rrons more readily and thus exhibit posilive oxhl:uion states equ:tl to the sum of
the 7.r. fxl. and .Sfelectrons: Ac(lll). Th(IV). PuiV). U(VIl. ;,nd Np{VIIl. As in lhe first
transilion series. this trend reaches a maximum at + 7. and lhercaflcr Ihere Is a
tendency loward lower maximum oxidlltion Slates (see Tabl.: 14.3). A reduced tendency 1o use .Sfelectrons as o ne progresses alone lhe :tclinide series is app;trenl: U(l ll)
may be oxidized with water. Np(Jll) requires air. and Pu(l ll) requires a strong
oxidizing agent such as chlorine. The + 4 stnle is the highest known for curium.
berkelium. and californium. and beyond these elements only +2 and +3 oxidalion
states have been subslanti;sted. Nobelium is actually more stable in solution as No!
lhan No'+ (cf. vtr).
The aqueous chemislry of the + 3 :tn!l + 4 actinide ions is complicated by their
tendency 10 hydrolyze and polymerize. Hi&hcr oxidation stales are represented by
stable actinyl ions (e.g., MD; .
unll
The Lanthanide and Actinide Elemenh
603
114
'E
109
.2
6 7 8 9 10 II
Number orI elc<:crons
12 13 14
Fig. 14.5 tonic r:Jdii (C.N. - 6) of Sc'. y>. L:r. Ln'. und
The lanthanide
and Actinide
Contractions
ions.
As a consequence of the poor shielding of the 4f and 5/ electrons. there is a steady

increase in efti-clive nuclear charge ami concomitant reduction in size with increasing
atomic number in each scrics.4l Although this trend is appiU"ent from the alomic ratlii
<Fig.
il is best shown by lhe radii of the t-3 .:ations tFig. 1-1.51. There arc two
notice:blc differences between I he two series of ions: (I) allhuugh the :octinidc contraction initi.llly parallels thai of the lanthanides. the elements from curium on are
smaller than might be expected, probably resulting from poorer shielding by Sf
electrons in these elements: (2) the lanthanide curve consists of two very shallow a rcs
with a discontinuity at the spherically symmetrical Gd)+ (4/7) ion. A similar discontinuity is not clearly seen at CmH
A consequence of the lanthanide contr.sction is that when holmium is reached. the
increase in size from n
S- n 6 has been lost and Hol + is the same size as the
much lighter yl+ ( 104 pml with correspontlingly similar properties. 44 The contraction
docs not proceed sufficiently far to include ScJ+ (88 pm). but it.s properties may be
from the lanthanide series. anti in some ways it provides n bridge
between the strictly lanthanide metals and the tr.msition metals .
, Sec Chuptcr 18 fO< n:llltivistic considern1ions .

.. F Olher consequences. sec Chapter 18.
The I orbitals
The
f orbitals have not been considered previously except to note that they are
ungrrade (Chapter 2) and that they are split by an octahedral field into three levels,
(Chapter II ). A complete set of seven 1{orbitals is shown in Fig. 14.6.
As with the d orbitals, there is no unique way of representing them, nor is there even a
way which is optimum for all problems. Thus Fig. 14.6 presents two sets. a "general
set" and a "cubic set." The latter is advantageous in considering the properties of the
orbitals in cubic (i.e., octahedral and tetrahedral) fields.
11R, 12J<, and
DiHerences between
the 41 and Sl
Orbitals
As with other orbitals of the same type (same 1), the 1{ and Sforbitals do not differ in
the angular part of the wave f\mction but only in the radial part. The Sf orbitals have a
radial node which the 4f orbitals lack, but this is not likely to be of chemical
significance. The chief difference between the two seems to depend on the relative
energies and spatial distributions of the orbitals. The 1{ orbitals populated in the
lanthanides are sufficiently low in energy that the electrons are seldom ionized or
shared (hence the rarity of lanthanide +4 species).
Furthermore, the 4fclectrons seem to be buried so deeply within the atom that
they are una1fected by the environment to any great degree. This point will be
discussed further below. In contrast, the Sfelectrons. at least in the earlier clements of
the series, Th to Bk, are available for bonding, allowing oxidation states up to + 7. In
this respect these electrons resemble d electrons of the transition metals. Because of
the higher oxidation states in the early actinides, it was once popular to assign these
elements to transition metal families: thorium to IVB (4) , protactinium to VB (S) , and
this arrangement was incorrect
uranium to VIB (6). In 1944 Seaborg suggested
and that the clements following actinium form a new " inner transition" series analogous to the Janthanides ..SThis suggestion, known as the "actinide hypothesis; was
useful in elucidating the properties of the heavier actinides and was fully substantiated
by their behavior (notably their lower oxid:ltion states) and electron configurations.
Nevertheless, we should not lose sight of the feet that in the earlier actinides the Sf
electrons arr available for use and that these clements do show certain resemblances
to the transition metals.
Absorption Spectra
of the Lanthanides
and Actinides
The absorption speclra of the lanthanide + 3 cations are shown in Fig. 14.7. These
spectra result from f-f transitions analogous to the J- J transitions of the transition
metals. In contrast to the latter, however. the broadening effect of ligand vibrations is
minimized because the 1(orbitals in the lanthanides are buried deep within the atom.
Absorption spectra of the lanthanide cations are thus typically sharp and line-like as
opposed to the broad absorptions of the transition metals.
The absorption spectra of a number of triva.lent actinide ions are shown in
Fig. 14.8. They may be conveniently divided into two groups: (I) AmJ .. and heavier
actinides which have spectra that resemble those of the lanthanides; and (2) PuH and
lighter actinides which have spectra that are similar to those of the lanthanides in some
ways but exhibit broadening resembling that seen in the spectra of the transition metal
ions. Apparently the greater .,exposure" of the Sf orbitals in the lighter actinide
clements results in a greater ligand- metal orbital interaction and some broadening
., Seaborg was warned no1 10 publish his new periodic lllbk bcauK il would ruin bis scie1'1lllic
reputation. He is qUOted as sa)li"'l sometime bier, " I diem' I have any scienlilic reputation so I
published it .,yway." For a discussicn of lbi$ and oilier iruoresli,. hislorioa.l devdopmcn<s in
actinide chcmislty, see
Kautfi!WI's review, " Beyond Unniwn" in Clkm. Eng.
1,_,
68(47), t8-29.
The cubic oet
Theaenc.rtJttt
hrsptlve drawln&
Ptnpe<:tiv< 4nwlnJ
crou-tion plot
Cl<>,_etion plot
,.
,.
Contour plot
... uontwboc
lz axis
(A ttion tw Ntn
C'Ul out
cut out of &he I*O
"coolar1" for darlly.l
or lhe rwo
"'coU.an''(otdatlty.)
r
x) Samt as,, excepJ lies atonal hex uls
y' Slmt N t 1 ucepc Iits alon& che y axis
_---
xt'
xl' l1'1
1
X
1(31'-x'l
r(x'Y'l
xyr
I
I
Same ux(x 1 3y 1) . .eeptlies alone they axis
Sameuthecomspondln&orbitalsin IM C\Iblcoet
xyr
--
>..
:;;illlfi:"=" <
<:000
OOC)
I
lbl
,,,....,
2
t(x
;t
!i
::1
a..
-Y l } S.mc as IM xyr but rotated 4S 0 bout
X(t 1Y 1 l
the x. , y, and taxes
(ll
Fig. 14.6 The/orbitals: (a) plo1s or rhe angular pan or the wave functions or the/orbitals; (b) contours of a 4/orbital. Dots indicate maxima in
10"/. or maximum. ((a) From Friedmn . H. G .; Choppin, G. R.; Feurerbacher. D. G.
elecrron density. The lines are druwn for densities which
J . Chtm. due. 1964,41. 3S4-3S8. lb) From ()gryzlo, E. A. J. Chem. due. 1965,42, ISO.. IS I. Reproduced with permission.J
..
it
'"
::1
;:
!;
Ill
606
14 Some Descriptive Chemistry of the Metals
11'.
3.0
Jo 18 26 24 n
20
18
16 14
12
10
F.._.,cy (kK)
Fig. 14.7 AbS()rJ>tion Spectra of f'r' . Nd'. Pm'. sm, Eu'. Th1 . oy'. Ho,.. Et'.
Tm'. Yb' in dilute acid solution. Compare the sharpness of lhese with that of Ti'
(Fig. 11.11), a ftrst-row transilioo ebnmt . [Modified from Camall. W. T .; Fields. P.R. In
Fields. P. R. ; Moeller. T .. Eds.; Advances in Chemistry 71;
Americun Chemicnl Society:
OC, 1967. Reproduced with permission.)
The lanthanid and Actinid E l -
607
F"tg. 14.8 Absorplion spectra or trivalent aclini<lc ions in dilute acid solution. (From Camilli,
W. T . : CrossWhite:. H. M. In Thr CIH:minry
Ac:tinidr
G . T.; Morss, L R. Eds.: Chapman and Hull: New YIJI'k, 1936:
permission.)
Kaaz. J. J.: S..abors,

Reproduced wilh
from vibrational elfeelS. As the nuclear charge increases. the Sf orbitals behave more
like the 4f orbitals in the l:mlhanide.'l :md the spectra of the heavier actinides become
more lanthanide-like.
Mognetic Properties
of the lonthanides
and Actinides
We observed in Chapter II that the paramagnetic moment of the lanthanide ions

(Tabk 11.251 could be calculated from lhc
g(JIJ + Ill! tEq. 11.-Ul. This
:tppnY.tch is su.:cessful because spin-orbit coupling is
and unly the ground state is
popul:uc.l. Ligand tick! ellects arc small becau....: Ihe
orbilals oo not effectively
intcr..ct with the ligands of the complex. For SmH aiKI EuJ . spin-orbit coupling is
nul large enough to prevent occupation of the lirst excited stntc at room tempe.rature,
but if one includes this occupation in the calculation. good resulls are obtained.
The flllll.!netic properties of the actinides are quite complex. Whereas the spinonly formula (ligand field effects large compared to spin-orbit coupling) gives reasonable results forthe first-row transition compounds. and Eq. II ..II (spin-orbit coupling
large compared to lig;l.nd field effects) gives good results for the lanthanides. neither
formula is adequate for the actinides. The Sf electrons of the actinides interact much
more: with ligands than do the 4Jelectrons of the lanthani.les. As a result the spin-orbit
coupling :md ligand field effec.ts are of comparable magnitude.
values of
the parnmagne1ic moment vary with temper.llure and in general are lower 1han those
or the corresponding lanthanides.
-v
6t8
14 Some Descriptiva Chemistry of the Metals
Coordination
Chemistry"
Comparison of Inner
Transition and
Transition Metals
The lanthanides behave as typical hard acids, bonding preferentially to fluoride and
oxygen donor ligands. In the presence of water, complexes with nitrogen. sulfur. and
halogen (except F - ) donors are not stable. The absence of extensive interaction with
the 4forbitals minimizes ligand field stabilization energies. The lack of LFSE reduces
overall stability but on the other hand provides a greater flexibility in geometry and
coordination number because LFSE is not lost . for example. when an octahedral
complex is transformed into trigonal prismatic or square antiprismatic geometry. Furthermore, the complexes tend to be labile in solution. Table 14.4 presents a summary of
tl1ese differences based on properties of typical transition metal complexes.
One noticeable difference is tlle tendency toward increased coordination numbers
in the lanthanide and actinide complexes. This is shown most readily by the earty (and
hence largest) members of the series when coordi.n ated to small ligands . The structures o f the crystalline lanthanide halides, MX3 , exhibit this effect. For lanthanum,
coordination number 9 is obtained for all of the halides except Lal3 whereas for
lutetium, only the fluoride exhibits a coordination number greater than 6. The coordination number of the lanthanide ions in hydrated salts in which the anion is a poor
lipnd tends to be 9 as shown by many X-ray studies. The nine water molecules in
IM(H20M1 + are typically found in a tricapped trigonal prismatic arrangement. The
degree o f hydration in solution, however. has long been debated and many early
Table 14.4
Camporison oltrCiftsitioft
metal ians ond lanthanide
ions
Metal orbitals
Ionic radii
4/
106-85 pm (1.06-o.ss
3d
pm (0.7H.6 AJ
A>
Common
coordination
numbe.r s
Typical
coordination
polyhedra
Bonding
Bond d irection
Bond strengtlls
6. 7, 8, 9
4,6
Trigonal prism. square

antiprism, dodecahedron
Square plane, tetrahedron,

octahedron
Little metai-Ugand
Obital interaction
Little preference in
bond direction
Bond strengths correlate
with etectronegativity,
decreasing in the
orde.r:
011. H20,
Strong
r.
No;.cr
Solution
complexes
Ionic; rapid ligand

exchange
orbital interaction
Strong prefere.nce in
bond direction
Bond strenglhs determined
by orbital interaction,
normally decreasing in
rotlowing order:
NH1 ,
OW, r
Often covalent; covalem
complexes may
exchange slowly
" Kamiker, D. G. /. Clrm. Educ. 1970. 47, 424-430.
46
For a discussion or the coordination chemistry ol'the lanJhanidcs, see Han, F. A. In Compulrnsiv
CoqrdinaJion Clrmistry: Wilkinson.G.; GIIIard. R. D.: McOeverty.J. A . Eds.; Pergamon: Oxford.
1987: Chapler 39. Th Chmristry of tlr Actinidt Elmmts ; Katz. J. J.; Seabora, G. T.; Moru,
L. R.. Eds.; Chapman and HaD: New YOI1<. t9U; Vol. 2.
Coordination Chemistry
609
experiments led to the conclusion that the degree of hydration decreases in progression along the series. Evidence came from several kinds of data such as the partial
molal volumes of the hydrated lanthanide + 3 ions.47 As the central ion decreases in
size, the partial molal volume decreases as expected until crowding of the ligands
becomes too intense. At this point (Sm), a water molecule is expelled from the
coordination sphere and the molal volume increases temporarily before resuming (fb)
a steady decrease (Fig. 14.9). Luminescence lifetime studies have been interpreted to
give formulations for hydrated E:tr+ and Tb3+ ions in solution of {Eu(H20)9.ho.31H
and {Tb(H2019.o:to.3 l 3+
(n these studies the experimental reciprocal lifetimes of
ions in their excited states (T- tl can be correlated to the number of water molecules in
the first coordination sphere (Fig. 14. 10). It was suggested that the larger ear1y
lanthanides have coordination numbers of 10. while the smaller, later lanthanides have
coordination numbers of9. As shown in Fig. 14. 10, the number of coordinated water
molecules diminishes as they are replaced by oxygen chelating ligands such as nitrilotriacetate (nta) and ethylenediaminetetraacetate (edta). Recent neutron diffraction
worlc. however, is in agreement with coordination numbers of 9 and 8 for the ear1y
lanthanides and 8 for the later ones.49
Separation of the
Lanthanides and
Actinides
The early separation of the lanthanides was beset by difficulties as a result of the
similarity in size and charge of the lanthanide ions. The separations were generally
based on slight differences in solubility, which were exploited through schemes of
fractional crystallization. The differences in behavior resulting from a decrease in ion
F"19- 14.9 Partial molal

\'Oiumes ol hydrated ur.
18.0
lines represeru suagested

I'Mne- and eight-coor
dination. The hydnued

Sm,. and Gd,. ions
rei'O"esent equilibria between
the two species. [From
Spedding. F. H.; Pika!.
M. J.; Ayers. 8 . 0 .
J. Phys. Chrm. 1966. 70.
Rei"""duced
with pennission.J
2440-2449.
!.0
116
108
tOO
- r(pml
<7 Spedding.
F. H.; Pika!. M. J.; Ayers. 8 . 0 . J. Phys. Clrrm. 1966. 70, 2440.2449. For a current
discuuion. see Rit.kalla. E. M.; Cboppin. G. R. In HDIIdbook"" rlrr Physics and Clrnnistry ofRou
Eortlr.s; Gsclmeidncr. K. A.; Eyrina. L. Eds.: North-Holland: Amsterdam, 1991; Vol. U.
pp 393-442.
4f Horrocks. W. DeW.; Sudnid<. D. R. J . Am. Chrm. Soc. 1979. 101.334-340. Horrocks. W. DeW. ;
Sudnick. D. R. Ace. Chrm. Rrs. 1981. 14. 384-392.
49
Helm. 1..; Mert>ach. A. E. Eur. J. Solid StaU lnorg. Clrtm. 1991,28, 24S-250.
61 0
14 Sollie Descriptive Choniatry of the M.tala
Fig. 14. 10 A plot of

vs. mole frxtion of H,O for
Tb(llt) solutions. Here we see a cOdination number of 9 for Tb(UI) in contrast to
a coordination oomber of 8 sllown in rljl. 14.9. Experiments like these suaest tbat perl>aps
the early lanthanides ba>'e coordination numben of 10 while the later ones have COdi<oalion
numbers of 9. In the prqm<:e of a qu..tridentate tipnd. nilrilouiaceta te (nta). four water
molecules are lost and the number of coordiN!ed water rnolct>IH drops 10 five. When
ethylenediamineteuaacetaJe (ecb), a heudenl&le liaand. is .dded. the number of water
molecllks drops 10 three. (From Horrocks. W. DeW.; Sudniclt, D. R. Ace. Ch<m. R<s. 1911.
14. l84-:w.!. Rep-oduced with permission.!
radius along the series are commonly attributed to a decrease in basicity. reflected by
a decrease in solubility of the hydroxides. oxides, carilonates, and oxalates. The
fmctional crystallization and fractional precipitation methods are extremely tedious
and have been replac:ed by more efficient techniques.
The decrease in basicity (or more realistically. the increase in acidity) of the
lanthanides provides an opportunity for employing coordinating ligands to effect
scP"r.uion. Other things being
the more ncidic a c01tionic species the more
readily it will form a complex. In prnctice. the IDnthanidcs arc: placed on un ionresin and eluted with a complexing ngcnt. such as citrate ion or ahyl.lroxyisobutyrate ion." Ideally. the complexes should come off the column with minimum
overlapping of the various bands (Fig. 14. 11 ). Such processes have incrensed the
or lanthanides available and opened up mnny possibilities for commercial use
le.g. rare-earth phosphors for color television). The initial separaliuns of many of
the actinide elements as they were synthesized were effected by similar methods.
l anthanide Chelates
The stability of lanthanide complexes cnn be increased by menns of the chelate eft'ect.
and much earty work was directed townrd the elucidation of the stability of the lanth:.onide cbelates.sz The results nre only partially interpretable in terms of simple
,. A< we sh:>ll sec below, these "other lhi,.s" may be e.aremc:ly compli.::oled.
' ' K&IL J. J .: Mons. L R.: Seaburs. C. T. In 1M Cllmutry qftll' ltctinld'
K.:ttt. J. J .:
Mon.<. L R.: Scablrg. C. T . EeL<.: Cb:lpman ancl Hall: New Vert. 1\11!6:
pp llll - 11)3.
:o: Moeller. T.: Mmin. D. F.: lbompson. LC.: F<miS. R.: Fel111ei.C. R.: R:lnd:oll. W. J. C,.,m. Rrr.
1965. 6.S. I-SO.
Coordination Ch..,.istry
Tm
lu
Tb
Dy
Ho
14.11 Ek11ion of
trivalem lanthanide and
actinide ions on a Oowex
SO cation-exchaiiJlt
&I
()d
with an amm011ium
ahydroxyisobulyrate
duonJ. 1l>e band for Lt'
is predicted. [From Katz.
J . J.; Morss. L. R.;
Yb
l.
20
100
50
Seahorg. G . T . In
of''"'
Elt'mt'nts; Katz. J. J.;
Morss. L R.; Sea borg,
soo
200
I ll
(b)
G . T ., Eds.; Clwprnan nnd

Hall: New Yort< . 1986;
Vol. ! , pp 1131-1133.
Actinide
611
tJMd
""'
Es
cr
Reproduced with
Bt
permission.!
Cm
Am
II
II
II
II
II
10
:!0
.su
llrt
soo
1<1011
mooels . Figure 14. 12 portrays the relative stabilities of variuus lunth.,nide chelates.
Two types oi behavior may be notaJ:jJ (I) "ideal" bchuvior exemplified by chelates of
ethylenetliaminetetruacetate (etlta) and the closely related trttlf.t l.::!cyclohexanediand t!) " nonitle:tl" behavior us exemplified by diethylenetriamincpentaacetate tdtpal complexes. The former conforms to OtJr expectations
based on
elcctrost:Jiic or acid-base concepts of size and chur,;e (a more or less
uniform in.:rcasc in st:tbilily al'Cllmpanying 1hc dccre:\se in ioni.: r:tdiust . The discontinuity :.11 gad111ininm llhc "gadolinium bn:ak") .:oukl be :tltribntablc to the dis.:on
tinuity in crystal mdii at this ion or. more plausibly, hoth may rctlc.:t small LFSEs
assoei:ucd with spliuing of the
liflcll f orbitals. Thc position or yttrium on
these stability curves is that expected on lhe
or its size- it fans very dose to
dysprosium.
h;llf of the ligands th:1t have I><: en studied in complexes with
Unfortun:Jtely.
all of the lamhanides show discrepancies from the simple picture presented above and
must be considered type 2 ligands. In gener.>l. these may be characterizal as having
usually
stability/atomic number curves similar to type I for the lighter
wilh a break at gadolinium. The behavior of the heavier lanthanides is variable.
no change in stability, sometintcs even showing
however. often showing
stability with
;uomic number. Furthermun:. the placement of
n This cmvtio:ation i< adcqu:>te for the ""'"'"t discussi<tn. hul

second catcgo<y into two clas.cs: - Footnote 52.
$4 This
alllhor. furlher <Ubdiidc the
behavior is ideal in the sense !lull it follows our pr<'OOI'ICeived notion of what slmuid ocour.
612
14 Soone DMcriptiwe Chemistry of the Metols
Fig. 14.12 FormaJion

constants at 2S c for 1: 1
chelatcs of Ln,. ions
with various aminepdycarboxylate ions flda,
iminodiaoetatc; nta, nilriJo..
triacetate; , N-hydroxyethylethylenediaminetriacetale; edta, elhylenediaminelelruacelale; cdta,
trans-1.2-cyclohexane.
dinmineletraacetate; dtpa,
dicthylenctriaminepentaocetate). (From Moeller, T.
J.
Educ. 1!'70. 47,
pcnnission.)
yttrium on these wrves is variable, oflen falling with the pre-gadolinium elements
rather than immediately after gadolinium as exJ>ted on the basis of size and charge
alone.
Several factors have been advanced to account for the unusual behavior of the
type 2 complexes. First, ligand field effects might be expected to influence the position
of yttrium, since it has a noble gas confiauration with no d or f electrons to provide
LFSE. in contrast to all of the lanthanide ions except od' and Lu1 +. Obviously,
however, this is insuffiCient to account fo r the variable results for the Thl+ -Lu1
complexes. A second factor is the possibility of coordination numbers greater than 6,
which may also vary along the series. Thus it is entirely possible that an effect similar
to that seen previously for the degree of hydration is taking place. At some point along
the series the decrease in metal ion size might cause the expulsion of one of the donor
groups from a muhidentate ligand and decreased stability . This point could be reached
at different places along the series dependin& upon the geometry and steric requirements of the multidentate ligand. It should be remembered that the thermodynamic
stability of complexes in aqueous solution reflects the ability of the ligand to compete
with water as a ligand and that the observed trends will be a summation of the effects
of the lanthanide contraction, etc., on the stability of both the complex in question and
the aqua complex. For this reason it is not surprising that the situation is rather
complicated.
Lanthanide and actinide complexes. Ln(L-L)l and An(L- L)4 , of sterically hindered Jl-diketonates (e .g .. (Me,CC(O)CHC(O)CMe,r (dpm) and (F1 CCF2CF2C(0)CHC(O)CMelr (fod)), are of considerable interest because of their volatility.
Despite their high molewlar wei&hts, they have measurable vapor pressures at temperatures below the boiling point of water. This volatility has been
in
F"og. 14.13 Proton NMR

spectra (60 MHzl of
t-lleptanol . (a) Spectrum
or O.l M 1-heptanol in
coo,. (b) Spectrum
20
IS
10
Oppm
or 0.78 moror ratio or tris(dipivalo)llmethanato)e uropium(llll/1-hcptanol in

CDCI,. [From Rabenstein,
0 . L. ltna/, Chem. l!nJ ,
41, IS99-160S. as modific11

by Mayo, B. C. Chtm. Soc.
Rtv. 1973, 2, 49-74.
Reproduced with
permission.)
separating the lanthanides by means of gas chromatography.'' In addition they have

applications as antiknock additives; in tl'liCe an:llysis, solvent extraction, and vapor
plating of metals; and as homogeneous calalysts."
Perhaps
such as dpm and fod have atl1'11Cted greatest attention as
NMR shill
In 1969 Hinckley discovered that the complicated proton NMR
spectrum oC cholesJerol is greatly simplified in the presence of
Simplification occurs because chemical shifts are induced by the paramagnetic lanthanide ion. An example of the effect is shown in Fig. 14. 13. The proton NMR
spectrum ofhepJanol, without ashifl
is very complicated because of accidental overlap of signals (Fig. 14. 13a). In contrast, a spectrum of Eu(dpm);, solution in
heptanol shows the resonance of each set of equivalent nuclei as independent signals
(fig. J4.13b). Although the availability ofhigh-lleld NMR instruments has reduced the
need for NMR shifl reagents in organic chemistry, applications to biological systems
(lipid bilayers, proteins, ion mobility) continue to grow."
The Transodinide
Elements
At one time it was considered extremely unlikely that there would be any significant
chemistry for elements with atomic numbers ereater than about 100. The nuclear
stability of the trnnsuranium elements decreases with atomic number, so that the halflives for the heaviest elements (Table 14..5) become too short for fruitful chemical
studies (i.e. , 11 ,.. seconds).60 However, advanced chemical techniques have helped
'? S'oeven.
R. E.; Bsooks. J. J. ;
J. A.; Rhine. W. E. In Inorganic Compounds with
PTopntwl; Kif11, R. B.. Ed.; Advances in Chcmislry ISO; Amerieon Chemical Society:
Wasllincton. DC, 197'6; pp 122- 231 .
"'Wenzel. T. J.; Williams, E. J.: Halliwa111er. R. C.: Sievers, R. E. Polyhtdro11, 1985,4, 369- 378.
S7 Hort. F. A. In
Chtmhtry;
J. A., Eds. ; Pcrpmon: Ollf'onl. 1917; Jll) 11110-llO.S.
sa Hindley, C. C. J. ltm. Chttn. So<. 1969. 91, .S l60-.SI62.
G.; Gillard, R. 0 .; McCieverty,
"Wiliams, R. J. P. Sml<t. llotldin, (Btrlin) Jttl, J(), 79-1 19. LontltDttilk PToiHs in
O,,mkol
ond &nh Sdmtts: Tlttory tmd Prtict; Buoali. J .-C. G .: Oloclpin. G. R.. Eds.; El$cvier:
Amslctdam, 1989.
00 No ooly arc the ...,.-.Jives short. bua in some: instances il is not
ooe alom per wedt!
10 produce more lban about
614
14 Some Descriptive Chemistry of the Metols
Tobie 14.5
Hoff-lives of set.ded
actinide nuclides
Actinium
Thorium
Protactinium
Uranium
Neptunium
Plutonium
Americium
Curium
Berkelium
Californium
Einsteinium
Fermium
Mendelevium
Nobelium
laWTencium
Rulhetfordium
Hahnium
UnniU1exium
Unnilseptium
89
90
91
92
93
94
95
96
en
98
99
100
101
102
Mon......_
Half-life
227
232
23t
238
237
21.8 yr
1.41 x 1010 yr
3.28 x to yr
4.47 x rov yr
2.14 x ro yr
24, 150 yr
239
241
248
249
249
253
257
lOS
256
255
256
257
260
106
263
107
262
103
104
433
yr
3.4 x ro' yr
320 days
350 yr
20.5 days
100 days
1.27 h
3.1 min
31 s
4.3 5
1.5 s
0.9$
4.7 ms
CMmistry
Actinilk Elm,.nls; Kalz. J. J.; Seabota, G. T.; Morss. L. R.. Eds.:
Chapman and Hall: New Yorlt, 1986; Vol. 2.
u
elucidate information about these elements. More promising is the oullook for funher
synthesis of transactinide elemeni.S. With the synthesis of 10tMd, u12No. and to)lr in
the years 1955 to 1961,the actinide series was completed. Since then six transactinide
elements. u14 Rf(l969), tosHa (I <riO). tOt>Unh (1974), to7 Uns (1981), 108Uno (1984). and
uwUne (1982), which are congeners of hafnium, tantalum. tungsten. rhenium. os
mium , and iridium, have been synthesiucJ.fll Claims for element 110 have not been
confirmed.6l There has been much SJ>e{:ulation over t he possibility of stable
of
even higher atomic number. Theoretical calculations on the stability of nuclei predict
st:tbility for atomic numbers SO, 82, 114, and 164.fiJ The prctlktion is home
out for
which has more stable isotopes than
other clement , :mJ for M:l'h :10<.1
M,Bi . which
the heaviest clements with nonradioactive isotopes. The stahility \>f
nuclei in the regions of t!le ''magic numbers" has been describetl
by
Seaborg as mountains in a sea oC instability. as shown in Fig. 14. 14. The expected
stability is proportional to the elevation of the islands above "sell level." The peninrunning "northeast" from lead represents the decreasing stability of the actinide
elements. The predicted island of stability at atomic number I 14 and 184 neutrons may
American nnmes :.re nobdium (102). lawrencium 1103), rutherfordium ( 1041. and hahnium II OS).
Soviet worltc.. have suacsJed joliotium ( 102), kurchotovium (IQ.I),
ncilshuluium ( 1051. Tbc:ir
Gennun
have prcposcd
11071.
liM). nd mcitncrium (10'1). No
n:ome luis yet been suacsted fOC' elem<nl 106. Dispulc: 0 - who flr.;t discovcr<d clemcnl! 102. 103.
IQ.I. and lOS continues. Dapni, R. CMm.
t992. 70()7). oi-S.
: Kauft'man. G.
El!g.
1990. 611 (47), 18-29.
.., Sec Scahora. G. T.: Keller. 0 . L. Jr. In Th.- Cl,_mistry 10/ tiM Artini.lr Elcmcnu; KaiL. J. J.:
Sc:aborg. G. T. ; Mons. L R . Eds.: Chapman and Hull: New York. 1986: Vol. 2. Chapter 2 .
" Future Elements."
Fig. 14.14 Known 3lld predicted regions of nuclear Slobilily surrounded by a sea of
inslability. lfrom Seabora. 0 . T. J. Cfltm. Ed11c. 1969, 46, 626-634. Reproduced with
permission .)
be accessible with new methOds chat make i1 possible to "jump" the unstable region
and form these nuclei directly. Thus one might expect to find a group of relatively
stable nuclei in the region of elements 113- I IS. The possibility ofjumping to the next
isl:md (nol shown) at :uomic number 16ol provides even more exciting (and improbable) pussibilities to extend our
of the chemi:llry of heavy elements.
Periodicity of the
Tronslow rencium
Elements
Lawrencium completes the

series :md fills I he Sf sel of orbit.nls . Rutherfordium and hahnium would be expected to be congeners of hafnium and tantalum and to
be receiving electrons into the 6d Or'bitals. This process should be complete at clement
II:! feka-mcrcury).
then the 7p orbitals would fill from clement 113 to clement 118.
which
be another noble gas element. Elements 119. 120. and 121 should belong
to Groups lA ( 1). IIA (2). and I JI B (3). respectively. The former two will undoubtedly
have l!.st and
configurations. If the following elements parallel their Iichter congeners. we might expect 121 (cka-actinium). to accept one 7d electron und the
follo wing clements (.:ka-actinidcs} to procecJ with the filling oft{ Or'bitals. Unfortun..tdy. wc know very lillie <!OOUI the relative t:nergy
for thesc hyputhelic:ll
atoms cxccpl th:U1hcy will be .:xrremcly clnoc . 'Thus. all hough Fig.
wnultl predict
as the order of tilling: 8$, 5JI, t-.f. 1<1. /Jp, etc .. it nul known whether this would be
lollowed or not. Calculations intlkate lhat t he levels are so close together that
" mixed" configurations (analogaus tu the SJ 14/n configurations found in t he lanmay
For this reason it does not
thanides) such as f>i!IJ/ 1Sg" or
seem profitable to speculate oro the sepunuc
or the S.ll'w and 6/ 14 series.
Seaborg has
that the two series be combined into a l:!rgcr series of 32
ell!ments called t.h e sttpuac:tiniut':r."' His revised form of the periodic chart is shown
in Fig. 14. 1S. The
Sg elements form an extra long "inner transition" series
clements ( IS4-162) with filling of 1d
foDoweu b)l (presumably) a sene.\ of len
orbi1als. elc. Magic number nuckus 164 woultl thus be a congener of lead (dvi-lcadl.""
S.r
w Mxocl. J. U.; W>bcr. J. T. J. 0..-m. l'lrys. 1975. JJ.
., SeahorJ_ 0 . T. J . Ch.-m. EJ11r . I,.., -No.
,.. Since dcm<fll 164 would b;rvc :111 atotn< numb<t'

il be dubbed "twei Blci"l
lwicc lhal of t..d 11121. it bas been
o-
r--c
II
AI
I)
12
" Rb
,
n
c.
Fr
, Ct
Sr
8a
Sc
II
IC
,. y
" .u
"
Be
... "''
K
r;:i
La
....
., v ,. c. ""' Fe
"' Ru
Nb
Mo
Tc
"
b
Zt
41
Hr
Ta
IJ
Rr
Ha
..
Ro
1J
(1061 (1071
.
..
Co
Nl
Cll
It
II
21
..
Ca
Zn
'
Sl
II
F
10
,. ,. So
Co
Ar
)I
IC
"
u
Nc ,
Ar
II
Br
1(,
"
J2.
..
" .... .. Ha " n fse Pb u Bl n Po
lr
Oa
u
.. "' Rn
u
"
"
"
uoa1 <1091 UIO>l <IIIIJ<112>l<mlU141lum : ul6llu m:u JSI
-
lUI
..
PI
to
C4
A&
4.S
Sn
Sb
To
Xe
IJ
I)
II
i'
..f
Ill
0 19)' (120): (121) I (1 54) 1(ISS )I 1156): (IS7) I (158) I (IS9) I (160) (161) I (162) (163) (1 64) I (16S): (166) I (167)1 (168)
I
o
I
1
I
I
I
c
j
I
1
I
___l____L__l
L&ntloaJ\ida
Actinides
Suponctlftldes
rciiiiTcmiT(,;;,T--- - -- ---- ---- --l'f- -- --- - - ---- ---r,i's3i1

1L - .:_L
I
'
'\
- "'--- ---- - -- ------))-- - -- __ _ _ ____ L_..l
I
...l
f ig . 14.15 Lon1 form of Ihe periodic chan Ulended lo include hypolhetical

elements. Blocks with
shaded comers represent synthetic
(Np and Pu are found in nature in lrace quantities only). Blocks willl dolled
lines represent undisoovered elemenls. [Modified from Sebo111. 0 . J. Chtm. due. 1969. 46, 626-6)4. Reproduced wilh
permission .)
Fig. 14.16 Exlrapolaled

heat or sublimation
or
leold (114), from wllich. by

400
applicalion or Trout on's

rule, a boiliqg point of
147 "C is obtained. (From
Sc.aborg, G. T.; Keller,

0 . L, Jr. In Tltr C/trmi.rry
300
of 1hr Actinidt Elrmrnts:

Kll<t, J. J.; Seabora. 0 . T.;
Morss, L R.. Eds.;

Chapman and H..l: New
200
York. 1986: Vol. 2,
O.apcer 24. Reproduced

widl permission.)
tOO
While much of the pre<:eding is spulative, it is no more speculative chemically

than Mendeleev's predictions o( gallium (eka-aluminum) and germanium (eka-silicon).
The speculation centen on the possible or probable stability of nuclei with up to twice
as many protons as !he heaviest stable nucleus. The Iauer falls outside the realm o(
inorganic chemistry. but the synthesis and characterization of some of rhese elements
would be
welcome.
Several workers have predicted the properties of certain translawrcncium elements.67 For example, the "inen pair effect" should be accentuated making the most
stable oxidation states of eka-Ulallium, eka-lead. and eka-bismuth + I. + 2. and + 3,
respectively. Relativistic effects become so importanl for these elemenls that ekalead, with its 7p2 configuration, may be !hough! of as having a closed shell. Its boiling
point has been predicted lo be 147 c, based on heal of sublimBlion extrapolations
(Fig. 14.16) and application ofTrouton's rule. The possibilily offormingelements wilh
alomic numbers in lhe region of 164 is of considerable inleresl. As discussed in
Chapter 18, elements following rhe complerion of each new type of subshell (e.g. 2p6,
Jd 10, 4f 14) show "anomalous" properties. and rhus lhe chemical properties of dvilead should be equally interestina.
67
Scabora. G. T.; Kdleo", G. L, Jr. In 1M

tl/lltt ANinldr Elttrttnts; Katz, J. J .; Scabors,
O . T.; Mens, L R., Eels.; ())apman and Hall: New Yoci(, 1986; Vol.l, Cbapecr 2.4 and references
!herein.
618
1 4 So111 Dscriptin CMmislry of th Mtals
Problems
14. 1
Froncium has a smaller alomic radius than cesium and rudium il smaNer lban I>Nium.
Expi:Un. (See Pyykko, P. Chrm. RC'v. 1988. U. 363- S94.)
14.2 Accoum for the facl thul a 23% contrnctiOII or radii uccurs for 3d M' ions (Sc' to cu'>.
bur only a l%conlntctionoccurs in the 5dseries(Lu>+ to Au' ). (See Mason, J . J . Cltem.
Edttc. 1988, 6J, 17- 20.)
14.3 Arrnnge the followioc complex ions in order or increa.sinc stabifity: [AuF,r, [AuCt,r.
[AuBrll- . [Aulu. [Au(CNlzr. Provide a rationale for your series.
14.4 Pyridinlum chlorochromato: and pyridinium dichromate are wieldy used in organic: synthesis as oxidizing
What are the formulas und structures for lhese reagents? What
advontllges mi&ht they have over more conventionAl oxidl:tfnc llgCllls such as potassium
dichromate or poiOssium perri1UI&onate?
14.5
Ruthenium and osmium, unlike iron, form compounds with the metnl in the +8 oxidution
stale. Can you think or a nonmetnl that achieves a +8 oxidation state in some of its
compounds?
1"-6 Compounds of iron exist in which there lite 0, t, 2, 3, 4. and S unpaired electrons. Find an
eumple fa each spin slate. Oassif}' thC$C complo:xes as low spin or bigh
14.7 The tendency or a metal ion to form compounds of hiah coordination numbers decreases
across the first mw of the transilion elemeniS. Eltpi!UR.
14.8 CbromiumtVO oxide is sJf0111ly acidic. vanadium(V) oxide is amplloleric, titaruumiiV)
oxide is inat, and :scandium(JII) oxide is buic with some llmj)hoteric: propenies.
a. Explain the relative acidiiX$ of these oxides.

b. Wrile
equations which show the amphoteric ..aturc or vonadiumiV) and
sc=diumlllll oxides.
1
14.9 The powerful oxidizing sJrenath of 1FeO.J - is shown by its abili1y to liber.1te oxygen
from water and to produce dinitrogen fmm atnll'lOlflia. Write balanced cquntions for these
two reactions.
t.uo
The following high spin complexes or I .Zbis(diisopropylphospllino)elhane tdippe) have

been prepared: !Cr02 (dippe)h, MnOt(dippe). FeCiz(dippe), and CoCI:(dippe). Suggest a
slructure for each and predict its mQgnetlc moment . (See Hermes. A. R.; Girolami. G. S .
lnt>f11. Chern. 1988, 27, 1775-1781 .)
14. 11 a. The intense red of an [Fe(phen),l 1+ solulion i rcplnce<l by

sulftc is lidded to it. Explain.
blue when eo:rium!IV)
b. Whereas [Fe(phcn)(H 10 ll>+ nnd IFe(pbcn):t H1Ghl 1 ore pnrnmu1J11clic,

(Fctpheni,J1 Is diamagnetic. Exptin.
14.12 The complex, Ni(Pb2 PCH 1CH2PPh 21Br1 , is diomaancric . Suggest a slruCiurc. The
tion of
with nickel bromide represent s one of I he more
n>ethods for its prepanuion:
Br
Ni8r1
Br
"-.../
Ni
/"-...
PII,P
-\_/PPh.,.
1
2Ph 1 POi =CH1 - - - "'"'-"'
6 ""---+
:a mechanism for lhe formation of lhis complex.

Ncl..,.,, J . H. lnnrg.
19A9.18, 215-217.)
(See R.ohn. J. A.; Dclian, A.;
Problems
619
14.13 The reaction of cobah(lll chloridelhf in penlune whh ln.lrhurnyllithium affords

telrnkisllnurbomyllo:oball. What is the oxidizinc
in
n::>o:oinn? Expr<ss this
reuction with a chemical equation. Dr:lw the Slructure of I he <:Ompk:x. Rationalize the
observed masnctlc moment 12.0 BMl.
t4.1-' The
INi(Se.l:J: - and (ZIIISe.>,l:- have been churnctcrizcd."" The nickel complex
has n square planar aeumetry. butt he zinc complex is
Offer explalllltions as to
why the nickel complex is not tetrahedral nnd w hy the zinc complex is not square pla.,.or.
14.15 The re.oction .:>f Nilenl: l, with 1: yields 11 dlumacnctic complex or furmuL11i.:>n Niren):I.
Wlult is the oxidation s1n1e of nickel in this complu'! Is yourans\\crcunsisccnt \\ilh the
at>,cnce .:>f ;o magnetic
The complex.
h:os :als.> b<cn
is the
'llnlc of nickel in this
Expl;.in.
isolatcl.',.
14.1(o II is
IO isoltotc lrUIIl'Mn(l.-L):CJ: , II'IIIISIMntL-LI:CI:r . und trails
IMnll.-LI:O:I'. "hich have macncoi.:
of
) . IU. :ond ) .\19 BM. respectively. Cbssofy these complexes as low spin or hiah spin. IL-L os a bl<lent:>lc
H"w mit:ht
the Mn- CI hond
10 wry in ohos series?
tScc
Warren. L F.: Benncll . M.A .
Clwm.
1.1. J l2h-J I-IIl.l
'I'!'
1-1. 17 Tb.:
I '11\Jc:turc or ryrnziniun1 chlllrochr omatc has b..-.:n n:I'K't'IC<l.-. Oro1w Slru<tures
d 111.: '"'h<>n and anioo . H)drot;m bond in$ '"i"'' b<t\\ecn th.: 1\\ u oun.. Pn:dt.:tlhe Olloms
invuh<"d a nd .:omparc ) . - (ltl!<hction woth lloc o"'-:rvcd p;lllcrn.
1-1.1.11 Titanium rcxts " i th chlorine'" form Tiel, and TiC1 1 liow oni&ht )uu ..:p.,r:ue these"""
(ll'odocb? 1s.:..- Gn,..,hen.. T J.: Kl><hundt:. K. J. lllfn:. Cit m. 1990. !9.
1-1. 19 Huw would you fll''l" the futlowint;
a. IR.NJIVO.IMct'Nl,l
b. VCI!lPY I.o
c:. VCX."'_,Ip)l,
d. ll'h.fii:IVO,CI: I
c:. tR,No: IVCX'I,I

IScc Zh."nt;. Y.: llolm. K. II. 111"'11 Cltrm. I'J'Jt .?9, 1111- 1117. (.,.. l.:;tdiiiJ!
1_..20 The purple .Jillk!r.
<JCtahcdro1l
onlilh.lliun about lil;nium. Sus::c"'t o:1 octnctun! for
-.:OO'Ipk"< .
it paramagne1ic "'
tScc Hcrm.:s. A. K.: Oiml:omi . G. S l11.,r;: .
t990 . .?'1. J ll-317.)
a:-,,,
f'-1,
Jhi\ll,:ht
he
""" ntnv h<.:n J')rcran."\1 in n.tnu,aucuu' , ..
'fh.:
tboll ie " nut .a m1\tun: .,r 1-"d: :n'-' 1.'
in."iJUbilily.
could y,,.. prov.:
r\:U.'-OOS fur ib
1-t.!! ln,tttllh chh,ri,lc r&::t\'t' \\ ith u iriH:n)'lahu,pht"'= h t fuun tn;::un.11

umu
l'cl' l,oi'J>h,l 1><11 11i1h
ho 1'11:11 f"ol:okhcor:ohdral
orrcr .on c\pl n;otiun fur lhC'C \II\ICIIIr\11 J illi:rcnccs. ISec
J. 1>.: l'uli. K. lmm:.
Clorm. III'JO. :!.V.
t-4.23
wilh Mulium p.:nta,ulfi,ft! to furm nickd
hc"allh1runtck.:lai"'11VJ
J i,ullitk . . ,
K, Nil',, +
<
t'ln.-.ari. M. A.: Mhkr.
---+
t '.
NiS,
+ liS
II : Clxl'l!h><lc. (L S.: l.u . Y -J : lhcn. J. A. ''""" ('form. t!/911,
1.. R.: llil':l'on. S. J, 1-"v""'" W.: Wcl><lcr. M J .
('ltrltt. .\
IJ"I"'"
"' ""'"''..,-H:h. )1 , R.: Wilku. R. 1>.: I>,IIJI.llcr. W . w.: O:tnl. G. 1.. llwr11. (IINII. tii'JII. !9.
" Yoo>G. K 11.: Ko.:ho. J . K. 1"'''1: ( '/'""' 111'11.
" llunn.:u. 1'. R.: Sllit>ao. R. K.. K""<:r. It U. ,,..,..,, Clwm. t'IYII 'V.
I'M-I.
s;-
Co you lhink that Ni(IV) Is reduced to Ni(ll) ctdo you think that
disp'Oportionares to
and S? Wlult is the oxidation state oi nickel in NiS:? How do you know?
sz.-
14.24 Explain the emfs or the silver halides In terms oi their solubilities . Wha1 about silver
acetate, Which is scluble?
14.25 How can one verify, just by looklns at the Llltimer diaamm oi silVer. that sodium
lhioSlllfate (hypo) is useful in photosraphic procc:;ses that require lhe removal oi excess.
unreacted silver halide? Is this pr oceS$ (1\xina) ectuaUy a redox reaction? Explain.
14..21i When citina the Sandmeyer reaction. organic cbemistry te xtbooks frequently write the
needed copper(l) halide
as CU,CI2,
CU2 Br1 , etc . Comment.
14.27 Coosider the complex ions dibromoaurate(l) and tetrabromoauratc( lll). Which is more
stable in aqueous solution? Explain.
14.28 Explain in terms or redox chemistry how the formaJion ci chloro complexes stabilizes
menium(nt).
14.29 Predict whelher each
a. 2Fe,. +
b.
srr -
zcu> + 41-
- - 2Cul(sl
c. 2Cu>+ + 48r- c1.
oi the followina reactions wiD pruceed to lhe left or lhe ri&ht:

2Fct+ + sn
2Cu8r{s)
vo; + 21r + cu -
ll(s)
+ S r%(1)
vo1 + c.J + HtO
14.30 Studies ofradioisolopr$. both natural and from fallout. in Mono Lake. California. showed
tlult tGsr,
ll"J>b oc:cur a1 lower levels than micht have been expecled. Some
actinides such as "'"Th. noP:I, llOIU, and >>pu OCCWTcd at hiJher levels than expc<:tcd, but
others such as =hand 141 Am did not. The most notable cNracleristic or Mono Lake is
ils hich alkalinity (pH 10) caused by larae amounts oi carbonate ion ( -<1.3 M). Susgest
facton that may be responsible for these relative abundances.
14.31 If you did not answer Problem 10.8 When you re:od Chapter
tO. do so now.
14.32 In Ibis chapter we have referred to the synthesis of heavy actinides. Take a trip to the
library and answer the followin& questions:
a. Americium-243 can be obtained in kiJoir.un quantities. Write an equation for a nuclear

reaction for its preparation.
h. Nuc.lcar reactors allow ' 19Pu to be produced by the ton. Write a nuclcar equation for its
synthesis.
c. Elemenlt. 107. 108. and 109 have been produced by a method known ns "cold fusion."
Describe this method.
14.33 Plutonium-239 is nn extremely rndiooclive alpha emitter. Shieklina from alpha radiation,
however. is easily accomplished with thin paper. Why then is llPu considered to be a
dangerous isotope?
n Simpson. H. J.; Trier. R. M.; Touwaler, J. R.; Mathieu, 0 .; Deck. 8. L ; Glxn, C. R.; Hammond.
0 . E.; Full..-. C.; Ku. T . L Sewn 1912.216. 3t2-SI4. Andenon, R. F .; 81Con, M. P.; Brewer.
P. G.
1911. 116. Sl4-316.
Prolll"'
621
14.34 Actinide ions oll.cn form .cidic solutions as a result of hydrolysis:

M(H,G); ----+ M(H 10),_ 1(0H)'.-n
the following sets of cations in order of their tendency to undcrao hydrolysis:
a. Pu
w. Pu,.
b. Ac,.,
lJ'. 1'111 , Cm1
14.35 Theo'e is no physiological process for plutonium removal from the body. Various chelaling
agerus have been used as 1herapcutic reaaents for its removal.> One of lhesc. shown
below, is a tctracatcchollipnd.
OH
OH
n=l
OH
OH
Speculate on bow Ibis tipnd binds to Pu.

14.36 Panmapelic: ions may aller N MR chemical shills by what Is known as a c:ontact shift or
by what is known as a pscudocontact shin. Consul! an NMR book and explain the
dill'e rence.
14.37 Anhydrous LnX, can be, prepared from the reacllon of L n metal Ollld H&)(1 Write the
balanced equation for tbi reaclfon . Can you name an auractilll! feature of this reaction?
When aqueous sotUiions of Cel, Dtld CeCis are concentrated,
and
CeCI,(H,Ol.. respectively. crystoaiu. Sugest sttuclures for both salts. Do you think
heating these salts mi&hl be a &ood route for prcparina anhydrous CeO, and CeJ,?
14.38
GouJcs made of didymium (a
of P r and Nd) arc prefer red for sfassworkins to

absorb the glare from sodium. Explain why these aoa&Jes are more suitable than a pair
made with Til+. for example.
14.39 Biochemisu sometimes thin k of Ln,. ions as analoaues of col+ . Discuss reasons why
there might be a resemblance between
and
Any notable differences? In Who!
ways might biochcmiSis exploit a resemblance?
Ln'.
74
c..
Raymond, K. N.; Smillo . W. L Stru.t. &Ntdfnf (BtrllnJ I981. 41. 1$9-186.
622
14 Some Descriptive.Chemistry of the Metols
.I
-100
!1:
<I
-200
Fig. 14.17 Variations in

standard enth:llpy changes.
Mr. nt298.1S K for
reactions of lanlhanides: (a)
M 3 .(aq) + edta4 -(oq) M(edtnnaq); <bl MCI,(s)
+ !CI!!g) ..... MCI3(s); (c)
Mfs) +
MCI3(s).
Open and closed circles
re,..eseru estimated and
experimenlal values
respec1ively. (From
Johnson. 0 . A. J. Chem.
EJ11c. t980. 57. ifTS-471.
ReJl"OOOCCd with
permission.)
L>Cc Pr NdPmSmEuGdTbDyHoErTmYbl.u
14.40 There h:ls been a 1endency 10 view lhe lanthanide ek:menls as having nearly iden1ic0ll
cbemis1ry. In recent times Ibis view bas been crilidzed." Standard enthalpy changes for
1hrce reactions are ploned in Figure 14.17. How do you accounl for lhe dramaJic
shown in plols (n) ;md (b)? Cnn you p<ovide an cxpluMtion for the " bumP"" ut
Eu and Yb in plol (c)'!
"Johnson. D. A. J . Cbt>m. Ed. 19110. 51. 47S-4n.
Chap
er
15
Organometallic
Chemistry
A n organometallic compound is generally defined as o ne thai possesses a mdal-
carton boncJ.t The bonding interaction, as delineated by thejoum31Orgonamewl/ics,

must be "ionic or cov:llenl. Jocali:tetl or
between o ne or more carbon
:ttoms or an organic croup or molecule and a transition. lanthanide. actini.Je, or main
Gf'OUP metal :ttom." Despite this r:uhcr risoroos definition. the bonlerlines that distinguish orcanomewllic chemistry rrom ocher br:tnche:s an: sometimes unclear. For
example. all chemists woui.J
nickeltetracarbonyl.
as an Oq!anometallic compound even though carbon roonoxille is h:m!ly a typical
organic compound. Likewise ors:tnuboron. ori:'Jnosilicon, orpnoarsenic . :tnd org-.lll<>tellu rium compounds :trc included in oraanumclotllic
even though boron,
:mil tellurium nre boro.h:r1ine metals.
inort!anic: chemicals
silicon.
such as sodium cyanide. ahhoush
n mc1akarbon bon.J. are noa normally
categorized as or&anumetallic
Organometallic chemistry can be viewed 01s a bridge between
and inorganic chemistry. On the pmctk::ll
billion .Jollllr.
rc1.1lized rrom
inllustriul pruces.o;cs h lililing honHI&eneuw
llascd <In ors;onometallic chemistry in 19l!.5. and it is pre.Jictcll that the r11lc of urgan<lffit:tOIIIics in the pro.Juction uf
phm maceuticals. UJl.richcmicals, flavors. rragrau-.:es . semiconductors, and cemmic
precursors will continuo: to
du ring t he
Organumetallic catalysts
.,. ,,s
' Then: art a number ol valuable S<lUr<:<S which c::.n proviok varic.J p<rlii>CCiivu on a .Jclinition fO<
O<piOI!lCf:lllic c:llemWry a well as cx!X'n<led c:ovcmse of vir1ually every topic included in this
dlapocr. See: Elscllenllroich. C.:
A. ()rgGfiOfn<IDUkl. 2nd ed.: VCH: Wcinhcim. 1992.
Cnhlrcc:. R. L Th
Chrmi.<lry <if tlw Tmnslthm Mrmls: Wiley: New York. 19118.
Powc:ll, P. l'rlrrciplcl t1{0rJ:UH<>f<'WIIic Cil<'mistry;
:>nd Hull: t...lncloo. 19!18. Thnycr. J . $ .
Clrrmis try: VCH: New Yurt. 111811.. Colm;on. J. P.: Hq.W.. l . S .: Nonun. J . R. :
Finke. R. G. l'rinc;ipks uJ Aptlli<Dti<HU u{ Orl(tJMirtlftSit/dft Mrtul crmulry. !nol
Univcnity
Sc:imc:e Boob: Mill Volley. CA. 19!17. Pur1dns. A. W.: Polcr, R. C. An lntrtl<lmtH>n tu
0fJl<Jtt011f("tal/lc Cltrmistry: M:ocmilbn:
t911b. Yun:tm01o. A. lkl(turiJirunAiti<>n Mdal
Cltrlflistry; Wiley: New Yo<lt. 1\1116. Lul<cluon. C. M. FmftforrwiOiul Tru iUitiutl Mrtal Or_.olic
Ownr#rry: lltoolts/Cole: Mt.,.ercy. CA. 19115. C-.rw<"hrllfi'Y OrJ/IlMimrrallk C/k'mistry; W"dkin
son. G.: Stone. F. G. A.. : Abel. E. A . Ed>.: l'et1llltllun: OxfonJ.
: P:wshall. G. W. Ori!G-tullicl
tm . 6. 1187-$2 and private C<llMllrooicalion.

62l
424
15 O rg a nometallic O.emistry
will become increasingly impor1llnt in an age when temperoture (and hence fuel) needs
to be minimized in chemical processes. As petroleum reserves are depleted. it is likely
that such catalysts will play a major role in conver1ing synthesis gas, derived from
coal. into useful organic intermediates.
The 18-Eiectron
Rule
Molecular O rbital
Theory and the
18-Eiectron Rule
The first attempt to account for the bonding in transition metal complexes was made
by Sidgwick.J who extended the octet theory of G. N. Lewis to coordination compounds. Ligands were considered to be Lewis bases which donated electrons (usually
one pair per ligand) to the metal ion which in tum acted as a Lewis acid. Stability was
assumed to be nuendant to a noble gas configuration for the metal. The sum of the
electrons on the metal plus the electrons donated from the ligands was called the
effective atomic number (EAN), and when it was equal to 36 (Kr), S4 (Xe), or 86 (Rn),
the EAN rule was said to be obeyed. An alternate and more general Slatement is that
when the metal achieves an outershell configuratio n of nsZCn - l)d 10np6 , there will be
18 electrons in the valence orbitals and a closed, stable configuration. This rule of
thumb, which is referred to as the
mit, has the advantage of being the
same for all rows of the periodic char1, eliminating the need to remember a different
EAN for each noble gas. Funhermore, the number is an easy one to recall since it is
merely the total
of nine orbitals. one set each of s, p, and d orbitals. Because
the rule is obeyed with ralher high frequency by organometallic compounds, especially those having carbonyl and nitrosyl ligands, it has considerable usefulness as a
tool for predicting formulas of stable compounds.
As with most rules of thumb, the 18-elec,t ron rule is not always strictly obeyed: Stable
complexes with both more than and fewer than IS outershell electrons are fairly
common. 4 1nsight into the connection between stability of organome,tallic compounds
and the IS-electron rule-and a basis for rationalizing the exceptions-can be gained
by reviewing the molecular orbital description of bonding in complexes (Chapter I 1).
For an octahedral complex
11.20), the most stable arrangement will be that in
which all of the bonding orbitals (a .... t 1.,. I'... and 1J1tl are fully occu pied anti all of the
antibonding orbitals are empty. Since there are nine bonding moleculilr orbitals, this
will require 18 electrons, as predicted by the IS-electron rule. Complexes will therefore tend to adhere to the rule if they have large A,. values, makinc occupation of the
antibonding
orbital unfavorable. Included in this category are complexes or second
and third-row transition metals. which are never found to have more than 18 e lectrons
beyond the core MOs. There may well be fewer than IS electrons, however. if the
ligands do not provide stabilization of the /'ZR level by 1T bonding. This is observed for
complexes such as [WCIJ2 - (14 electrons).
(l!i electrons), [OsCtJ 2 - (16
electrons), and (PtF6 ] - (17 electrons) . Ugands such as CO and NO, which are high in
the spectrochemical series because they are good 1T acceptors, are very effective at
stabilizing the t'ZR orbitals. This leads to a larger A, value and an increase in the total
bonding energy (Figs. 11.27 and 11.28). As a result. octahedral carbonyl and nitrosyl
complexes are found to seldom depar1 from the 18-electron rule.
If A, is small, as is the case for first-row transition metal complexes, occupation
of the weakly antibondifl&
orbitals is easily possible. As a result, stable com-
e;
> Sidpiclc. N. V.
&crronlr Tltlory of Valtll()': Cornell u.->enily: Ithaca. 1927.
Milcbell. P. R.; Parish, R. V. J . O>tm. E.dw. 1969,46, 8ll-114.
The 18-(ledron Rule
625
plexes with,l9 electrons ([CO(H:O>,J>. 20 electrons

21 electrons
([CutNH 3),J- ). and 22 eleclrons ([Zn(NH,>hl 2 +) are well known. Trnnsi1ion me1als
on lhe left side of the periodic lable have few outershell electrons to begin with and to
reach a total of 18 may require more ligands lhan is sterically possible (the nonexistenl
[TiF9 }'- would obey the IS-electron rule). For lhese metals, slable complexes having
fewer lhan 18 electrons are thus fairty common: [Tif,J 2- (12 electrons), (VCI,J 2(13 electrons).
(IS eleclrons). etc.
The picture is somewhat more complicated for complexes of other geometries. In
the case of letrahedral tetracarbonylnickcltO), lhe four u bonds from the carbonyl
groups result in four strongly bonding molecular orbitals (a1 and t 2). accommodaling
eight electrons (fig. 11.21). The remaining len electrons must occupy lhe e and , ,
orbitals, which are formally nonbonding and antibonding. respeclively. Since 6,
relatively small. occupation of lhe antibonding level is no I energetically costly and the
complex is slable. With only four ligands (capable of con1ribu1ing 1wo electrons each),
any telrahedral complex in which lhe me1al has fewer than len electrons available
obviously will have fewer than 18 electrons in total in the molecular orbitals. Thus
tetrahedral exceptions to the 18-eleclron rule. such as lhe slable 13-eleclron species
are quite common.
tFeCI4
Square planar d 8 transition metal complexes are consistent exceptions to the ISelectron rule. The combinalion of eight metal d elec1rons and two electrons from each
of the four ligands gives a total of 16. Yet these complexes possess such high slability
lhat il is often said lhey obey a 16-electroll ntle. With 16 electrons, all of the bonding
molecular orbitals in a square planar complex are occupied (fig. 11.22); any additional
electrons would have a destabilizing effect because lhey would occupy antibonding
orbitals. The addition of one ligand (donating two electrons) could convert a square
planar species into a live-coordinate. 18-electron complex. and in fact. live-coordinate
are well known (see Chapter 12). Yet in many
complexes such as
instances the added ligand leads to a less stable complex.
In general, the conditiQns
adherence 10 the IS-electron rule arc an
electron-rich central metal (e.g. one that is in a low oxidation state) and ligands lhat
are good 1r acceplors.s
r.
Counting Sectrons
in Complexes
The IS-electron rule has remarkable utility for predicting stabilities and structures of
organolllO!tallic compounds. By counting the number of outershell elec1rons surrounding each metal atom in a complex. it is possible not only lo predicl whether the
complex should be stable, but in some cases, whether there will be meral-metal
bonds. whether the ligands will be bridging or terminal. etc. There are two popular
Jli'OCedures for electron counting. the so-called neutral atom and oxidation slate
methods. each with their ardent supporters. Either method may be used quite successfully. but care must be taken not to mix the two. In other words, a strict loyally to one
Jli'OCedure or the other is required when counling electrons in a particular molecule or
ion. The neutral atom method is perhaps more foolproof because it does nOt require
cOfTect assignment of oxidation states, which can sometimes be difficult for organometallic compounds.
To use either electron-counting procedure, il is necessary 10 know how many
electrons each ligand in a complex donates to the metal. Table IS . I gives electron
contributions for a variety of ligands for both tbe neutral atom and oxidation state
' Cbu and Holfmann have discussed some interestina exceptions lo the 18--dcctron rule in the conleXI
oC molecular ortiJal ddcriplions. Cbu. S-Y.; Holfmnnn R. J . Ploys. Clu!m. 1912. 86, 1289-1297.
o-
:;!
Tobl 15.1
"-- -- - -
sloli
electron
'lf 'f,": . Neutral atom

"-
electron count
....
Alkoxide (M-ORI
Thinlllle (M - SRl
Carbene alkylidene (M-CR 2)
Carbyne' . alkylidyne (M&rCR)
"'
( ...... _..
2
2
.... ,. 2
don"r if it runellons as
t.
Oxidation state
electron count
2
2
Th 18-EI dron Rut
627
methods. The electron count for neutral ligands is the same by either method: thus
phosphines and CO are listed as two-ele{:tron donors in both columns of the table . The
electron count for three complexes involving these ligands. CrtCOl,..
and
Fe(C0}4 PPhJ. would be
Cr
6e-
6CO
Cr(C0)6
Ni
10e4PF3
8eNi(PF3)4 18e-
12e18e-
The electrons counted for the metal atom in each of these complexes are those in its
valence s and (/ orbitals. Metals having odd numbers of electrons obviously cannot
satisfy the IS-electron rule by simple addition of CO (or other two-electron) ligands
because the resulling moiety will necessarily also have an odd number of electrons.
For example. MntCOJ5 and Co( CO) are both 17-electron species and, consistent with
prediction. do not exist as stable molecules. However, their corresponding anions.
[Mn<CO>sr and [Co<CO)J - . arc stable sp:ies and conform to the Ill-electron rule:
Mn
sco
charge
(Mn(CO),] -
fe-
18e-
Co
4CO
charge
(Co(C0)4]-
le -
18e-
(The count shown is for the neutral atom method . In the oxidation state procedure.
as an M- species and given an additional electron.
eoch metal woukl be
and there would be no entry for the overall charge.)
The dimeri.: species. Mn:<COJ 10 and Co21COJ,.. also are stable and are diamagnetic. If it is assumed that each compound has a metal-metal single (two-electron)
bond. the electron count yields a total of 18 for each
2Mn
lOCO
Mn- Mn
14<:-
20e2e-
Mnl<COito 36.:
or 18e-f Mn
18c2Co
16e8CO
")
Co - Co
-e
Co1 (C0)8 36.:or 18e-/Co
The molecular structure of the mansanese dimer dearly reveals t hat there is an
Mn-Mn bond tfig. IS. Ia. b). In the cobalt structure. two of the CO ligands arc
bridging. i.e .. they are simultaneously bound to both Co atoms (Fig. IS. tc. d) . This
does not alfcc.t the electron count, however. because CO and other neutral ligands
donate two electrons to a complex whether they are terminal or bridsing <Table IS. I):
Ill
c
I
M- M
c
1m
630
15 Orgonome talic Chemistry
more extended ., systems exhibit a greater number of binding modes. For example.
the cyclopentadienyl ligand may be pentahapto. tri-. or mono-:
@
I
1'-c,H,
TJJc,H,
M,o
TJ'c,H,
The power of the Ill-electron rule for predicting structures of complexes involving
unsatur:ued ligands can be
with
If both C,H, ligands were
pent3hupto. t he compound would huve 20 electrons. two more than the optimum for
stability. However. if one of the ligands is presumed to be pentahapto und the other
complex:
trih3pto. we have an
Thi5 preo.licted structure is ino.lccd the one observeoJ.&

FiMily, in applying any electron-countins procedure to organometallic complexes. we must remember that it is merely a formalism-albeitu very useful one. We
or the Illmust resist any tendency to presume that eit her method presented
electron rule for that maue.r, reveals anything about electron distribution in a
metal-ligand bond or mechanistic detuils about how a complex forms. Whill an
elcclron-countins exercise o.loes provio.le is a good first approxima1ion or the .ruhili1y
anti
of an organometallic complex. thus serving much the snmc fum:tion a' ..
Lewis diagram does for main group compounds.
Metal Carbonyl
Complexes
Almost all of the trnnsition metals form compounds in which c:1rbon monoxide acts as
a
There are three points d interest with respect to these compounds: II) Osrbon monoxide is not ordinarily considered a very strong Lewis base anoJ yet it forms
strong bonds to the metals in these complexes; (2) the metals are always in a low
most often formally In an oxidation state of 1ero, but some1imes 3lso
oxidation
in 3 low posi tive or nesative oxidation stute: and (3) as already discussed. the 18elcctron rule is obeyed by these complexes with rem01rk.able frequency. perhaps W/.
of the time.
Huttner. G.; Brinlzirlacr. H. H.; Bdl. 1... G.: Friedrich. P.; BCflicnkc. V.; Ncuscb-....,.., 0 .
J. Or,;nnonwt.
1m. 14,, 329.
Metol Carhonyl Complex
631
Formulas for stable carbonyl complexes formed by metals in the first tr.msirion
which will be discussed
series are given in Table IS.2. Several arc polynuclear
in a later section. Among the mononuclear compounds. the only exceplion to the ISelectron rule is hexacarbonylvanadium, VICO)h which is a paramagnetic. 17-elcctron
molecule. Interestingly. it does not dimerize to form the lklectron analogue to
and Col(C0l8 If the V :<C0l 1! dimer did form, it would give each metal a
coordination number of 7. which may present too much steric hindrance to allow
stability. Ligand repulsions may overcome a weak metal-melal bond or may provide a
kinetic barrier to dimerization. In any event. V(CO)h is less stal:lle than carbonyl
complexes obeying the Ill-electron rule. It decomposes at 70 "C and. if given the
opportunity, readily accepts an electron to form the IS-electron anion:
(15.2)
The molecular structures adopted by simple carbonyl complexes are generally

compatible with predictions based on valence shell electron pair repul.sion theory.
Three representative example.s from the first transition series are shown in Fig. IS.2.
1lle second- and third-row transition metals focm a number of compounds analogous to those in Table IS .!, e .g.,
Tc 2(C0) 10 and Re:<C0) 10 However.
between the first row and the heavier elements.
there are also some distinct
For example, the binary carbonyl complexes of niobium and tantalum. unlike vanadium. are unknown and. whereas tetrncarbonylnickd is stable. Pd(C0)4 has only
and Ru(COl, are less stable
been observed at low temperatures. Likewise
than Fe<C0)3 . The dinucleur non:ICOlrbonyl complexes of ruthenium and osmium.
and Os21CO>v nrc also less slable th;m their iron conscner. Fe2!CO)y.
lncreru;ing metul-metal h<md strength as one: desccn<ls a column of lhe periodic table
leads 10 much greater stability for OsJ(C0l1: :md Ru1 (C0lt! relative to their mononuclear M!CO)$ units than is the case fur Fe.7 lu fact. for burh Ru and Os. the most
binary carbonyls are the trinuclcar cumple:ote$. Despite the differ.,nces enumerated here. the resemblance of the firsr-row to the he-.1vier elements is probably greater
of coordination cumpounds.
for carbonyl complexes I han for other
Tobie, IS.2
Sloblo ccwbonyl complexes
of the lint-ow lt'onsilion
me lois
Muoonuclcar
Dinuclear
Trinuclear
Telranucleur
Hexanuctear
Cr(CO)h
Mn2(C0l 1.,
Fe<CO>,
Fe!(COlv
Fe)(C0l1:
NiCCOl4
CoiCOl12
COl,.
for the exisrcnce or V2(COI,! aJ 10 K hns been reported. Ford, T. A.; Hlber, H .;
KlotzbOch..-. W.: Moskovils, M.; Ozin. G . A . ltWrg. Ckr/fl. t976, 13, 1666-1669.
7 Unfortunately, the Slrc11J:Ih ofmctal-mctalll<>oos in rrnnsition melul cnmplc.,cs;,. hurd I<Hlctcrmine.

Fur in<lancc, the Mn-Mn bond
In M n,rC011o hos h<.>cn reported tu be ns low es 1>7 kJ
mol - 1 ;tnd u.< hi!lh as 172 kJ mol- 1 Pulsed
phoh>.-..:oustic calorimetry
the value
:u IS9 "' 21 kJ mot- and is consisfenr with rca:nt kin.:tic rosulls. Goodmon. J. I_.; !'.:ILT.I. K. S.:
Vaida. V. 0rJimlomnallkl 1986, S. StS-316.
oc,..---1'-co
c
0
Fig. 15.2 StrucllJres of the simple carbonyl complexes of chromium. iron. and nickel.
Preparation and
Properties of
Carbonyl Complexes
Some carbonyl complexes can be made by direct interaction of the finely divided
metal with carbon monoxide:
Ni + 4CO
Fe + 5CO
Ni(C0)4 (bp 43 c)
l'0021m
Fe(COls (bp 103 c)
(15.3)
(15.4)
Nickel tetracartlonyl is a highly toxic volatile colorless liquid that is shipped in

cylinders pressurized with carbon monoxide.8 Its vapor is about six times as dense as
air. Purification of nickel by the Mond process is based on the decomposition or
Ni(C0)4 , the reverse of Eq. 15.3. The yellow-red iron pentacarbonyl slowly decomposes in air and is sensitive to light and heat. In fact, F!::!(C0)9, an orange solid, is
by photolysis of Fe(C0)5 .
Fe(C0)5 --.!!!... Fe1(CO)y (mp 100 q
(15.5)
For most carbonyl complexes, however, the metal must be reduced in the presence of carbon monoxide:
CrCI1 + AI + 6CO
Rep, + 17CO
AICI,
:,::;'
AICI1 + Cr(CO>t, (mp 154 c)
7C01 + R!::!(C0)10 (mp 177 c)
(15.6)
(15.7)
In Eq. 15.7 the carbon monoxide itself is acting as a reducing agent .

Infrared spectroscopy is a particularly informative technique for characterizing
carbonyl complexes because of the direct connection between the number of C-0
absorptions and molecular structure. Another advantage to the method is that there
are few absorptions in the 1800-2200 em- window except for those arising from
C-0 stretching vibrations. We saw in Chapter II that the frequencies of these
absorptions can provide information regarding the carbon-oxygen bond strength in
coordinated CO. It is a straightforward matter to predict the number ofC-0 stretching bands expected for a carbonyl complex based on its symmetry. For a complex
such as Fe(C0)1 (011,). we would treat each C-0 stretching vibration as a vector
(Fig. 15.3) and then determine the symmetries ofthe set of vibrations by application of
methods outlined in Chapter 3. The result is that the vibrational modes include two of
Aj and one each of
and' symmetries, of which only the A2 and E are infrared
active, according to the Dllt character !able (Appendix D). Since one of these is
For a ltistorical accwnt of Ludwil! Monel's discovery or Ni(C04. the first met. I carbonyl C()mplex,
see Roberts. H. L J .
Clrrm. 1989. J72, t-14; Abel. E. lb/J. t990, 383. 11-20.
Metal Carl>onyl Complexes
633
It
I c
o=c- Fe.,..
I
c '
0
D:u.
r,a
lC1
2
3C2 a1,
I , 3
251
0
la,
l
Fig. 15.3 ldcnlification of the symmetries of the C-0 stretchlnc vibralions (represc:rued as
vectors) for Fe{CO),. The reducible n:prt5<ntlllion, r" is derived by counting the number of
vectors remaining unmoved during each operation Or the
point croup (sec Appendix D for
character table). Us irreducible components are obt:lincd by application of Eq. l . l .
nondegenerate and the other doubly degenemte, we expect the JR speclrum for
Fe(COJ, to show two C-0 stretching absorptions of unequal intensity (Fig. 15.4).
Infrared C-0 srrctching frequencies for mononuclear carbonyl complexes of the
first-row transition metals are given in Table 1.5.3.
Polynuclear
Carbonyl
Complexes
The dinuclear cobalt complex,

(Fig. 1.5. 1) represents a large number of
polynuclear carbonyl species containing bridging carbonyl ligands in addition to the
terminal carbonyl ligands found in all binary metal carbonyl compounds. The -C=O
representation implies that nCO licand bound to a single metal is relatively unchanged
from free carbon monoxide, i.e., th:llthe carbo n-oxygen bond remains a triple bond.
That the
bond order is approximately three in a terminal
ligand is reflected
in carbon-oxygen stretching frequencies: 2143 em- for free carbon monoxide and
2125-18.50
for terminal carbonyl groups.
Bridging CO ligands. on the other hand, are electronically much closer to the
carbonyl group of organic chemistry with a carbon-oxygen bond order of approximately two as found. for example, in ketones. Again. we may infer the bond order
from carbon-oxygen stretching frequencies, which are typically between 1850 and
c-o
co
em-
100.0
Fig. 15.4 Infrared

spectrum of the carbonyl
region for Fe.CO)s showing
the absorptions associated
with the Ai aod E'
atretchil11 vibrations.
83.3
"
'il
66.7
f!
d!
D .l
t6.7
Wow""""'"tt
(an' 1)
634
t 5 01'1JOOOftlelalic Chemistry
tS.J
lnlrorod c- 0 stretching
lreq....,cies of mononudeor
corbonyt complexes
Compoollld
c;-rry
Ni(C0)4
Tetrahedral
Fe(COJ,
Trigonal
bipyramidal
Triaonal
bipyramidal
Triaonal
bipyramidal
Octahedral
Octahedrnl
Octahedral
Ru(C0l5
(ls(COl,
OiC0)6
Mo(C0)6
WtC0)6
oe.-v..l
Point
group
c- o
mode aymmetries
IR o<!Wo
modes
'"*"'*'ci"
(cm- 1
Td
A 1, T2
2125 tC04l
2Ai, Ai. '
A,
Tl
A"2
D"'
A.; .'
A"]
DJJo
2Aj. Ai. '
A"]
01,
A,. r,.
r,.
' '
o,
2045 .
2002 (liquid)
1979
1999(C1 H 1J
203S
2006 (vapor)
2047
2000 (VapO<')
2003 (vapor)
1998 (v01porl
A,
r,.
r,.
r,.
r,.
Br:>!trm:ln. P. S. M<tal Carl>ottyl $p<C1ra; Academic Pteu: London. 197$.
1700 em- for bridging CO ligands. compared with 1715 10 em- for saturaled
ketones. It would be false, however, to think of a bridging carbonyl group ns a ke1one.
The M- C - M bond angle is 90" or less. compared to a C - C -C bond angle of
about 1:?0" for a n organic ketone. Funhermore. a bridging CO ligand is almost always
accompanied by a metal-metal bond. which leads to extensi ve delocalization in the
M -C -M moiety involving overlap of metal orbi13ls with both tr un<l .,. orbitals of CO
(Fig. 15.5). The infrared spect rum of a metal carbonyl compound provitlcs impor1<lnt
informatiun on the nature of the C3tbonyl groups present :m<l may allow one to
distinguish between a struc;tu re with only terminal carbonyls. such as
and
one containing one or more bridgifl! carbonyl groups, such as Ca:ICO),.. Noh: I hat
altem:uive 11!-electron structures may be drawn for these two
ganese decacarbonyl with bridging croups antl
octac.a rbonyl with none. as
shown in Fie. 15.6. Allhouch the bridced di=nc:mese compound is unknown. Ihere i.'
infr.ucd evidence thnt in solution the dicobalt compound exists :rs an equilibrium
in Fig. 15. 1d.
mixture of three isomeric forms. one of which the
conmins
Saructurcs of the other two isomers :are unccrt:ain but
Fig. 15.5 Overlap or C1 and

"orbi1nls ol bridging
wilh l he d
otbilals ol me1al nloms. The

v Ofbitnl of CO C:ltl donate
electron density 10 lhe
me1al
and lhe
emply .,. orbi1al or CO can
accept electron densily
rrum the d orbitals. [From
Kosik. N. M.:
R. F. ; lnCI'fl. Clr<m. 191J,
12. 666-<>71. RcproclJCed

wilh permission.[
N. M.: Fenslce. R.
Cltmt. t91J. n, 66t>-671 .
Metal Carbonyl Complexes
635
oc\
oc-r
/co
OC/Co\Co
CO
11>1
(dl
Fig. 15.6 Altenuuive structwes f dimanpncse decacarbonyl and dicobalt octacarbonyl.

Structure (a) is unknown. but then: is infrared evidence for the ex.istence of (b) in solution.
cartx>nylligands. One possibility is shown in Fig. I 5.6b."' The brid{!t!d form is the only
one observed in the solid state. however.
The dinuclear manganese and cobalt carbonyl comple.x es. as well as a number or
similar compounds. may be
on the grounds thm the 17-electron mononuclear units must form a meml-metal bond in order to provide each metal atom with
18 electrons. There is anOther group of polynuclear cartonyl complexes that may be
regarded as "carbon monoxide deficient" in the sense that they can be construcled
from the simple binary comple>tes by replacing one or more carbonyl groups with
metal-metal bonds. For example . in addition to FetCOJ,. Table 15..2 shows two Other
and lriiron dodecacarbonyl.
.:omplc:xes uf iron: diiron nona.:arbonyl.
Fe)IC0) 12. These .:ompounds. as well as rhc lclmnuclear Co.tCOl12 obey the 18
clc.:tron rur.: if metal-metal bonds arc included in Ihe formulations:
2Fe
9CO
M- M
16er8e2e -
36eor 18e-fFe
3Fe
12CO
3M- M
24e-
24<:-
6e-
Fel(C0)12 54
or 18e- /Fc
4Co
12CO
6M - M
36c-
2-k '
12eCo_.(C0) 12 72eor r8e-/ Co
Withmlt n\CJ:II-mclotl h<mds. these

would have 17. ln. ;tnd 15 electrons per
metal atom. rcsp..'Ctivcly. The deliciencics ;m: cumpcn-.ated b y one. lwo. and lhrce
M-M bomls per metal. Srructures for tbc two iron
arc shown in Fig. 15.7.
In the tetmcobah complex. tho: four metal atoms are arranged in the form of a
tetrahedron with the Co atoms occupyint: the comers and the six metal- metal bonds
forming the edges. Larger cluSters such as Co,.tCOl1,. are aL-;o known. but the ISelectron rule breaks down for comple xes with more than four metal atoms . In these
species. electron delocalization is extensive . and other models !described in Chapter
16) are of greater value."
' " Dor. G .: l>ictk:r. U. K.: Noa.:k, K. J . C'hcm. Sm. Chrm. ('.''""""'
Li<htcnbcrscr.
D. L.: Umwn. T. 1.. tn..rs:.
111711. 17. IJI!I-1:1112. F.Uiot. D. J.:
H. A .: PW<lcphall.
N. H.: Xiu. W.
Chc-m. 19119. ZIJ. 3282-J:!ll).
N. J.: Hobh. D. G.: HUhc<. A. N .:
Juhn.<on. 8 . F. G .: Paris4ni. E. Jm"N Clllm. Act a 19'12. /98-100. 34S-H9.
'"'''I:
II
W:l<k:. K. AJ. /ruws:. Ct.m.

1976. IH. I. Minf!O", D. M. P. 1kr. Clwm. Res. 1984.17,
311-llll. Mint:<>S. D. M. P.: Johnston. R. L.
HmJittN (/hrlinJt9R1. M. 29-M7. Teo. 8 . K .
('Ire,... t9KS. :U.
John-.ton. R. L.: Mirtt;os. D. M. P. /n..rs:. Chcm. 1986. ZS.
IMI-11>71. Wale>. D. J.: Millios. D . M. P.: Slcc. T.: Zhc:nyng. L An. Cht-m. Rt.t . t990. ZJ.
17-22.
636
15 Orgonometollic ChMistry
tal
...
ng. 15.7 Stereovitws lldll and converuional compulct' plots (ri1>tl o(

(a. b) and
Fc,(CO), (c, d).
B. F. 0 .; Benfield. R. E. In Tupics
and
OrganotrwtnJIJc
Oeofrroy, 0 . L.. Ed.; Wiley: New YOI'k. 1981. Reproduced
wilb permission. I
Whereas the IIH:Iectron rule is of great aid in predicllna metal-metal bonds. it

does not assist us in distinguishing between bridging and lerminal CO ligands, inasmuch as the electron count is Ihe same for either mode of bonding. Polynuclear
carbonyls both with and without bridging CO units are common. Among those lacking
CO bridges are M:(C0! 10 (M a Mn. Tc, Re), MJ(C0) 11 (M - Ru, Os), and lr4(C0l 12
New carbonyls of osmium [e.g., Os4(C0) 14 , Os4(CO).,, Os4(C0) 16,
Os,{C0>19 Os6(C0) 18 Os6(COh1 0s,(COJ:!1 OsJC0) 23] are being discovered with
regularity and all found thus far are essentially nonbridging. tl
A beautiful series of tetranucle:1r osmium complexes,
and
Os4(CO>u has been prepared (Fig. IS.8). tl Consistent with the IS-electron criterion,
these complexes have 4, S, and 6 metal-meta.! bonds, respectively. In Os4(C0) 14, four
of the carbonyl ligands :1re weakly srmibridglng and ten are nonbridging. The term
semibridging is used to describe CO ligands that :Ire unequally shared between two
metal centers. making them intermediate between terminal and bridging in their
ligation.
n Pomeroy. R. K. J. Orj,>atJOmn, Clrtm. 1990, JBJ. )87-411 .
"Johnston. V. l .: Einstein. F. W.
B.; Pomeroy, R. K.
LJII, 7, 1867-1869.
14 Cellon, F. A: Wilkinson, 0 . .Advat1ud /IIINA'DIIIc Clltmistry, 31h cd.; Wiley: New Yk, 19113:
"" 1028-1032.
Metal Cori>onyl Co111plean
637
Fig. 15.8 Structure.s o( lbree ldranudear osmium c:ari>onyl complexes: (a) Os.(COI,.. (b) Os.(CO).,. and (c) 0s.(C0), .
Di.m nces are in picomeJers. Broken lines indicale semibricl&i111 CO li&ands. (From Johnston. V. J.; Einstein, F. w. B.;
Pomeroy, R. K. J. Am. CJ..m. Sec. 1987, 109, 8111-1112 (a); J. Am. Chnn. Soc. 1987, 109, 722G-m2 (b); and
Orronomtallics 1988, 7, 1867-1869 (c). Reproduced with permiss;o,.)
M a b M
a II 13
\.o.l
J)'1M1<t1ic .....co
a=b
a=13
a'3<M
13
avtb
'--..; ol
scoaibridiinJ ll, .CO
Weakly semibridging carbonyls, such as I hose in Os. (C0)1 are nearly linear but
show some distortion toward the second metal. Of course it is nol always dear
whether departures from linearity arise from Interaction with the metal or because of
packing forces in the crys1alline solid. All CO ligands are fully nonbridging in the
puckered
described as a metal carbonyl analogue of cyclobutane. u The
dark rw cryMals of Os4CCO)., possess nearly planor Os4 unils with only terminal CO
ligands.
The existence or both bridged and nonbridaed forms of Co2<COla in solution
reveals how little difference in energy exists between the two isomers. The factors
causing carbonyl ligands to.bridge or not bridge are not at all well understood. Steric
factors are probably Important, for just as vanadium hexacarbonyl refuses to dimerize
(it would become sevei'H:OOrdinate), a bridged dimang:mese dec:acarbonyl would have
a coordination number of 7 or more (depending upon the number of bridges) rather
than 6. Not even a trace of a bridged dimanganese isomer has been detected in
equih'brium with the non bridged species, in contrast to the observations for cobalt and
iron. However. steric considerations do not acco unt for the common observation that,
"Jolvulon. V. J. ; &>skin. F. W. 8. ; Pomeroy, R. K. J. Am. Chrm. Soc. 1987, /09, 8111-1112.
638
15 Orgonometollic Chemistry
within a given family. the heavier congeners tend to have fewer bridges Ihan the
lighter ones. Thus FeJ(C0)12 [or FeJ(JL-C0h(C0l 11J
15. 7a. b) and
(or
(Fig. 15.9) are bridged and
and
(Fig. 15.9) are
unbridged. Although steric hindrance cannot be the explanation here, it may be that a
size effect of a different sort is operating. As the M-M bond lengthens (Co < lr). the
M-C bond must lengthen even more or the M-C-M angle must open up, or both.
Either of these structural changes could destabilize the structure, though it is not clear
that this is lhe explanation.
The remarkable carbon monoxide ligand can also bridge three metal atoms. 16
Four of the eight triangular faces in octahedral Rh6(C0lt 6 [Rh6(1'3-COl4 (C0ld

(Fig. 1.5. 10) contain carbonyl groups bridging three metal atoms. The corresponding
cobalt compound is thought to have a similar structure.l7
The elucidation of the structures of polynuclear carbonyls is a challenging area.
Bridging cnrbonylligands can often be detected via their infrared absorptions, but in
the case of complicated structures. spectral interpretation can be difficult because
sometimes other absorptions, such as overtones or combination bands. appear in the
carbonyl region. Infrared spectroscopy does have one advantage over methods such
as X-ray crystallography in the
to study structures in solution. which may differ
from those found in the solid state. X-ray crystallography provides unambiguous
information on structure but occasionally is beset with difficult problems arising from
disorder (see Chapter 3). A classic example is triiron dode=rbunyl, for which
disorder in the solid prevented a complete solution to the crystal structure for many
years.s The available X-ray data were compatible with a triangular array of iron
atoms and so a structure similar to that of the isoelectronic Os3(C0ltl which has only
,,/
ex co co
('f)
oc/
oc 'cc:6co 'co
..
Fig. 15.9 Structures of Co.(C0) 12 ,
and Jr4 (C0)oz.
CO hu"""" been shown to bind simullnncousty to four m<:ltllotoms. In thciHFe,(COt,.l- ion. for
campk:, th= Fe ato<M .,.c bound to n sinste CO throush the carbon atom while: fourth Fe
interacts wilh the., system. Carbon monoxide in this in.<tancc function. u. a four...:lcc:tron dnnot'.
Horwit.z. C. P. : Shriver. D. F. Ad>.
Cloem. l9fi.I.ZJ, 209-JUS. Adams. R. 0 .: B:obin,
J . E.: Tasi. M. lnorg.
19811. 17, 26ti!-262.S.
11 Chini. P. lnor/l.
1969. B. t206-1207.
11 A fascinating hi&toric:ll account of the process is provided hy O.:si<ler-to. It. Jr.: O<lbwn. G. R.
J. C/wm. Etfuc. 1981.59, 152-1.56.
Fig. 15.10 The Rh,(C01 16

molecule. Note lhnl four of
lhe fac:es of !he octahedron
formed by the Rh atoms
hllvc carbonyllipnds
llrid&i"' tltru rhodium
atoms. [From John son. B.
F. G .; Benfield, R. E.
In TO(>ics in lnOTflllnic
Dlld
SttrtuchtmiJtry; Geoffroy.
G. L .. Ed.; Wiley: New
wit h permission.!
terminal CO Jig;snds, w:u suggested. A weak band at 187S em- in the soli<l state
infrnrat spectrum of FeJ(C011: was
as Fermi reM>nance or as arising from
crystalline
rather t hun funtlamental
vibrdtion.,. The simple model
was finally overthrown by
evidence which proved thai the three :tloms are
not in K.lcntical environmcnts.tY Subsequent refin(menlof the
stru.:tun: showed
that the iron atoms do indeed form a nearly cquilutcrnl trinnglc. with one Fe-Fe pair
being brillgetl by two CO tigolnds (f ig. lS .7a. b).:O The solut ion structure. however. i!l
still ullller discussion. A n.- cent EXAFS stully o r frozen solutions
that
whether Fe,(COJ 12 exists as a fully unbridsell
or as a mixture of hriUg anti
unbritlgell forms Llcpends on the solvent.!! An I R stutly also suppor1s the existence of
a mhaurc of hri<f!)e<f :tnJ nonl1ridgctl stntcturcs in sohlli<>n.21 Th:u ahc molecule is
fluxional in both solution anti solid states .:ems cleu.r rmm a number of spectroscopic
inclulling IR m>c.l vari:tblcacmpcr:uurc NMR . Among the aucmpts that
h:tvc h.:cn made to du(idate the nature or this
rroccss :are stullic uf v;arioos
,lcrivarivc< If the Jotlc,arbonyl cOmflllllml. ! '
c- o
Corbonylote Ions
Numcrnu' aniunic curbonyl

"''" cullc<l carlm11ylatc ions. arc known.
These anions generally conform to the 18-clectron rut.: an<l arc interest because of
the information they proville regardins bond ing :1nd structure us well as for their
Llcrivative.. They ure often ch:clronically
usefulness in the synt.he sis of other
anti structur.ally related to neutrol carbonyl cumptcxcs (Table tS.4). For example,
or
Sec Gmndjc:tn. F.: Long. G. J.: Bcn:<On. C. G.: Rlls>. U. II'Jt. Clrrtn.
15!4-IS:!'J. fnt
ra:cnt
niiiY-'' uf t:.:oACOr .,.
""F.>r rcccN uto.c.votiu""< on rill: l ruo:turc Fc,tCf>lo: und cunor;ari_, with thai uf Fc: thiCOl 11
"""Chutl:hill. M. R.: l'cttiJIP'r. J. C. Orx""'"'"''"lli tm. 9,
" UiJWc:d. N.: Ev:.m. J.; Otc:lv.:s. G. N.; Price. R. J. J . Cit"' s..r. Clttm. C'"""'"" 1987.
tli,;cu"-'iun of the EXAFS mcth<Xl. ""' Chaplcr 1\1.
12 Oubo. S.: Nun&i:ontc-O:s;om. S.; Makcsc. M. lmtrJI. Cloim. Attu tllll4. 1/J. 167.
.,r
"' For""'"""*' SCI: l..cfttz. D.:
R. 0rl{on<llnd<lllict i WI . 10. 14117- 14116.
640
15 Organometallic Chemistry
Tab.. 15.4
Group
1V8 (4)
Group
VB (5)
0.""P
V18 (6}
VIII [7)
c.....,
Group
VIIIB (8}
[Mn(COJ,r
[Mn(C0)4 ) 3 -
Fe{COJ,
[Fe(CO>.J2 -
Complexes in the same column are isodoc:lronic; those in
c.....,
VIIIB (9}
GI'OIJf>
VIIIB (10)
[Co(COJJ-
Ni(COJ4
same row are both isoelecttonic and isoSUUdlJr.ll.
[Cr(C0J4t-, [Mn(COJJ 3-, [Fe(CO)J2 -, and (Co(C0J4r are isoelectronic and isostructural with Ni(C0)4 (F"tg . IS .2).
A common method of preparing carbonylate ions is reduction of a neutral carbonyl complex.
+ 2Na---+ 2Na+ + 2[Mn(CO),)-
(15.8)
Fe,(COJ.2 + 6Na ---+ 6Na+ + 3[Fe(CO)J2-
(15.9)
Mn2(COJ 10
Both of these reactions involve use of a strong reducing agent. In recent years,
reduction of cartlonyl complexes has been pushed to its limit with the synthesis of
highly reduced anions such as [Mn(C0)413 -. [Cr(C0)4f-. [V(COJ5J3 - . and
(Ti(CO)Jz- .24 Since (Mn(CO>J+. Cr(C0)6 , and [V(CO)J- were known to be relatively stable. there was some expectation. based on the 18-dectron rule, that it would
be possible to synthesize [l'i(CO)J2- . even though
is unknown. Often the
expectation that a product should exist is a long way from synthetic success. The
involved synthesis of [Ti(CO)J2 - illustrates the point.2S The overall reaction is
UU<Ct.,H, +CI)"JWUl m
Ti(C0h(dmpe)2 mco
(K(C222)h[l'i(C04,l
(15.10)
Potassium metal, which is a powerful reducing agem. reacts with naphthalene to give
potassium naphthalenide, another powerful reducing agent, which has the advantage
24
EDis, J. E. Adv. Orgonu-t. Clwm. 1m. Jl. l-SI. 8edc, W. Angnv. Clwm. Int. EJ. Engl. 1991.
JO. 163-169. Ellis, J. E.; Bars..-. P. T. ; Winzenburs. M. L; Warnock. G . F. J . OrgonmMt. Cl>mt.
1m. J8J. S21-S30.
Sec. 1988.110. 30}-304. Also

see EUis, J. E.; Chi, K .-M. J. Am. Clwm. Soc. 1m.112. 6022-123. for preparation ofJHf(CO).fby a similar method.
:u Chi. K .-M.; Frerichs, S. R.; Philson. S. 8 .; Ellis J. E. J. Am.
Metal
Complexes
641
of being dispersed throushout the reaction medium. The cryptnnd is added to coordinate rhe potossium ion. creating a b rge cution which allows isolation of the lnrll!e
31lion. There is evidence that uncoordinated alkali metal ions pc-event formation. or
stimulate decomposition. or
The reaction is run under Ar instead of
since rhe former is less reactive. Only carefully purified carbon monoxide can be used
because traces ofimpurities such as H 1 N!. or C01 compete in the reaction. Finally,
the reduction must be carried out at low temperaiUres ( - 70 q to minimize side
reactions. The product of this reaction is air sensitive (it rencts with 0,). as are most
carbonylate anions. Such reactions require special equipment such as Schlenk glass
ware or a glove box. which are standard items in any modern organometallic laboraIt shou ld also be noted that highly reduced anions may be shock sensitive, as
are
(M "' Cr, Mo. W) , K3[V(C0),1. nnd Cs,[Tn(C0)s].l7
Not all reactions leadins to cartx>nylate anions require strong reducing agents.
Some involve redUdion of the metal by carbon monoxide already pc-csent in the metal
carbonyl or disproportionation of the comple x. In fact. the first synthesis of a metal
carbonylate involved the former pc-ocedure:
( Fe(C0)4 ) 2 -
Fc(CO), + 40W -
2H2 0
(15. 11)
Often a Lewis base will effect disproportionation of a complex:

3Mnz(C0)10 + 12py--+ 2(Mn(py)6)l+ + 4(Mn(CO),) - +lOCO
(JS.Jl)
Mn2 (C0)10 + 2dppe - - + (Mn(CO)z(dppe)J+ + (Mn(CO),)- + 3C0(JS. IJ)

dppe = PhzPCH 2CH2 PPh1
The reaction with the relatively hard base, pyridine. has long been recognized as
disproportionation bur reaction IS. IJ with the softer phosphine base has only recently
been fully elucidated.211
Numerous bimetallic carbonyla te anions are also well known. Among them are
and [Ftz(C0).:J2 - , which are isoelectronic and isostructural with
Mn2(C0) 10 and
respectively.
Carbonyl Hydride
Complexes
Acidification of carbonylate ions often results in the formation of carbonyl hydrido

complexes. which may be regarded as the conjuaate acids of the carbonylales:
[Co(C0)4 J- + H1 0+
--+
[Re(COl,r + H 20
--+ HRe(COl,
[Fe(CO>.f-
HCo(C0)4 + H20
(15.14)
+ OH -
(J5_JS)
H2 Fe(C0)4
(15.16)
[HFeCCO>J-
The stronger bases can be protonated with acids that are even weaker than water.29
[Cr(C0l,J1 - + MeOH -
(HCr(CO),) - + MeO-
(15-17)
., Shriver. 0 . F.: Ore:zdzon, M. A. 1M Mo"ip11it11iun <J/ AiroSt iUitiw Cotnpunnds, 2nd cd.; John
Wiley: Nc:w York. 19116.
,., Wamoclt. G. F. P.: Spt;181JC. J.; f)arc, K. L.: EJias, J. E. J. Am. CMm. Sue. ti'U, f(}j, 6n.
u Kucbynka. 0 . J.: Kochi, J. K.
Clttm. 1988, 17. l.S74-:USI .
"'Darcnsboura. M. Y.: Oealon, J. C. l"ort Clrt m. 1981. 20, 1644-1646. Lin. J. T .; Haacn. G. P.;
Ellis. J. E- J . Am. Cltttn. Soc:. J91J. lOS. 2296-2JQ3.
642
1 5 Orgonometallic Chemistry
(15.18)
The reaction in Eq. 15.18 leads to a product with bridging hydride ligands; the nature
of the bonding in complexes of this type will be discussed laler in this section.
In addition to the protonation route, hydrido complexes may be prepared by
reaction of carbonyl complexes with hydride donors:
(15.19)
J-
[HF<(COl,f +CO
(15.20)
In a mechanistically similar reaction hydroxide ion can serve as the source of

hydrosen:
F<(COl, +OW -
[ F<(CO<J
J-
[ FOCO),(
IHF<(COl,r+ CO,
(15.21)
(15.22)
Addition of excess base in these reactions generates the dianionic starting material in
Eq . 15. 16. The intermediate shown in Eq. 15. 19. which has a coordinated formyl
sroup [C{O)H), has been isolated and characterized. Its counterpart in the OHreaction is a hydroxycarbonyl complex (see Problem 15.45). Both are inherently
unstable. decomposing to the hydrido complex by elimination of CO or C01 When
these
are auempted with Cr(C0)6 , the final product is not the expected
(HCr(COJ,J- anion. but rather a bridging hydride complex::m
an;
-
10
ol-
/
Cr(C0)3 C'-H
D:arensboura. M. Y.; DeaKln. J . C.
'""''B Chrm. 1981.10. 1644-1646.
(15.23)
Metal Carhonyl Compl....
__. (HCr!COl5l-
643
(15.241
+ CrtCOl, -
+CO
(15.25)
Hydri<le complexes may also be synthesized from rclate<l c:1rhonyl complexes or

directly from the elcmenl:ll metal. hydrogen. and carbon monoxide:
Mn!(C0) 10 + H! -
2HMn(C01 5
(15.26)
Co + 4CO +
HCo(C0l4
(15.27)
Complexes with :1 coordinated hydrogen atom are called hydritles whether or not
they exhibit I he chemical properties of u hydritle . Certainly compounds such as NaH
or LiAIH which SCf\1: as a source of H . are legitimutely called hydride. But many
of the transition metal carbonyl hydrides are. in fact. quite acidic . Buth HC<JtC01, and
HV1C01,. have acid
>imii<IT to that of HCI in water. i.e .. they :1re e"entially
complete!} dissociale<l in :1queous
At the
is such a
weak acid that its conju1!:ue base i rea-lily hydrolyzcd by w:l!cr !Eq. 15. 151. The
dihy<lride. H!FetCOI. WitS the first carbonyl hydride. complex to be s ynthesized.
been prcpare<l by Wulter Hi.:her in I'H I. his" yelluw Jiqnitl. unstuble above
-10 c. an<l bell:IWS as a dibasic acid in water 1pK 1 = 4.-1 :
E
1-11. The !urge
hy<lrogen
difference in the twu i<>nizatitJn ctJnsmnts provided the first evitl.:n.:e thai
aloms in th.: complex \\cr.: both huun<l lu lhc !kiRIC atom 1an<l hence to the iron atom).
The
values of a '""riety of mer:tl .::trbonyl hydride complexes arc ghcn in
Table IS.S.
Although in m:my
.:arbonyl hydride complexes
be rcgomletl as acids,
s how sum.:
to the bllsi.: hydrides llf the m:tin gn>up mcwls !e.g.
they
Toblo tS.S
Acidi.ltes of common
transition melol hydtidctso
Compound
pK0 (H,Oj
Compound
HVtCOt,,
HV!COI,I'I'b)
Hl"rCp!COI.t
HMuCP<CO>.
HWCp(COI_.
tiNruCOI,
,aronl'
H, RutCOI.,
liKuCptCOI:
HpstC0/4
HCoiCO),
HCo<COl_.IPPh,l
HCo!C'Ol,IPIOI'hl ,l
""
5.-1
6.2
X.t>
i. l
1!.9
13.6
4.4
11.9
IK.I!
HRctCOI,
H!FctCOl4
HJ'eCP<CO>:
HFcC'pICOl,
"
Mlu"'"' i"
HNiiPIOMel_,J;
HPd[PIOMe),J;
HPUP!0Mel3J.:
pK..(H,O)<
II.!
1:!.7
13.3
strong 10. \II

7.0
4.9
very wc;ok
5.9
3. 1
II
S. S .; N\lrhm. J. R. In
Afc<tnlllyJriJt'S: R,.,.,.,,,
unJ C.rt><'riJIIrt11: O..d;.,u. A. Ed.: VCH: New Yo<t . 1'1')2:
Ch11fl{.:r'J.
h
Cp - c,11, . cp
C.Mc .
lkc:wsc w;dcr is a .,.,.,.. ""'"""' for mo.tllrnMilioo mel I hydri<Jcs. :>eidil;.,,

w.:rc dclcrmincd frtlm equilibrium mca."urcments in :.cclonitrik: and pK._ values
in water wen es1imotcd from I he equutiun: pK.tH:OI pK.tcH_.CNI - 7.S.
644
15 Ogano-tallic Cbmistry
NuH. LiAIH.J. For instance, they can act ns reducing agents toward many organic
compounds and are capable of hydrogenating alkynes and alkenes. Thus their H li
gands are intermediate between the strictly hydridic hydrogens in the saline hydrides
and the protonic hydrogens in compounds with nonmetals (e.g., HCI. NH3) .
Hydride ligands bound to transition metals generally give proton NMR signals
that are considerably upfield from TMS (0 to -60 ppm). a feature that has been quite
useful in characterizing hydride complexes.31 For example, 1H chemical shifts for
and [HFe(CO)J- are -I I and -9 ppm, respectively, while typical values
for organic compounds are downfield from TMS (0 to + IS ppm). One should not
conclude, however, that the uptield chemical shifts in hydride complexes arise be
cause of high electron density about hydrogen. It is rather thought to be the result of
paramagnetic cont.ributions from the nearby transition metal.
The reaction of hydrogen gas with a transition metal complex can lead to a
monohydride complex. as shown in Eq. 15.26. or to a complex with two coordinated
H atoms. One of t he more famous examples of the latter is the reversible reaction of
Vaska's complex, lr(COli..:!CI (L = PPh3), with hydrogen:
H
L...._ i ....-H
(15.28)
....-lr...._
Cl
This reaction has the characteristics of an oxidative addition (page 689): The formal
oxidation state of lr increases from + I to + 3 and the coordination number increases
from 4 to 6. The process is believed to proceed via a concerted mechanism:
M+H2
_,.-1;1]
......
M,!
/H
- M..........
(15.29)
The proposed intermediate in this scheme represents an alternate mode of coordination for two H
a coordinated H. molecule. Although the intermediate in
Eq. 15.28 has not been isolated, a number of other dihydrogen complexes have been.
The first was prepared in 1983;12
Mo(C0)3(cht) +
+ H2
+ cht
(15.30)
(15.31)
(cht "' cycloheptariene)

The dihydrogen (')2-H 2) ligand in this complex exists with its H-H bond intact
(Fig. IS. I 1). Since the discovecy of the first H2 complex, many others have been
>I Cr.>btree. R. H.
0Tgonomnallic Cht mistry ofth TTansition M"als; John Wiley: New Yort.
t988.
:n Kli>as. Ci. J. Ace. Chnn. Rts. 1988,11. 120-128.
Metal Ccwbonyl Conlpl
645
Fig. 15.11 Structure o(

Mo{C0),(Pf'i.):,H 2 the fin t
nonclassic::ll dihydroaen
complex to be discovered.
(From Kubas, G. J. Jtcc"o
Clrrm. Res. 1988, 2/.
permission.)
characteriud. including some which for years had been presumed to be cis dihydrido
complexes.
It was not a simple mauer to prove that the complex in Eq. IS .31 should be
viewed as M(H 1) rather than
(see below). Even though it was possible to
grow a crystal and subject it to X-ray and neutron diffraction analysis. some questions
remained unresolved. Tile X-ray and neutron dota gave H- H bond lengths of 7S( 16)
pm and 84 pm. respectively. compared to 74 pm in uncoordinated H . These results
strongly suggested that the H- H bond had not been broken.
t he inherent
uncertainty associated with locating hydrogen atoms lefl some room for skepticism.
Synthesis of an 712-HOcomplex eliminated all doubt. The proton NMR spectrum of the
complex revealed an H- 0 coupling constant of J) .S Hz comparable to 43 .2 Hz for
uncoordinated H-0. The significance of these values is appreciated when they are
compared to hydride-deuteride coupling (less than 2 Hz) in complexes in which bond
distances are too great for an H- 0 bond to exist. In this Instance, it was spectroscopy instead of crystallography that provided the final confirmation of structure!
Complexes which contain the 772-H1 ligand are now referred to as nonclassical,
while those in which the H- H bond has been severed are called classical.
M-1
H
Tile difficulties encountered in firmly establishing the structure of the first dihydrogen complex still have nOt been entirely overcome. The H - 0 coupling constant
experiment described above offers a method or distinguishing between the classical
and nonclassical forms, but it is not applicable if the system is rapidly fluxional.
646
IS Orgon.,...etallic Chemistry
lnfr.u-ed analysis is difficult bec:wse M- H absorptions tend to be weak. Neutron

dilfrdo:tion requit-es large crystals. and Xray diffraction is not precise enough for
Jocatif18 H atoms. An NMR method has been developed for differentiating classical
and nonclassical structures that is based on the ossumption that hydrogen nuclei
involved in nonclassical coordination will huve significantly faster relaxation rates
than those involved in classical coordination.n In this approach, the measured spinlattice relaxation time. T 1 is correlated with the H- H bond distance and hence with
mode of coordination. Application of the method to the hydrogen adduct of Vaska's
complex (Eq. 15.28) and to
discussed earlier led to the conclusion that
both are best regarded as classiCII complexes. Recent reports have urged caution in
npplying the T 1 criterion, based on the finding that the ranges of relaxation rates for
classic:tl and nonclassical formulations overtap.)
The
bond may be profitably compared with a metal-carbonyl bond
since both involve CT donation to the metal by the ligand and both ligands can accept
-;;electron density into antibondiog orbitals. The
orbitals for CO an: empty
:r" orbitals. whereas for H. they are u- orbitals (Fig. 11.23). Like the C-0 bond.
the H- H bond is
as a result of t.h is metaJ- ligand 1r in temction. A strong
d- v inrera.:tion can sever the H- H bond and lead to fonnation of a classical
complex.
Some special note should be !rukle of the structure and bonding in complexes
conraining a bridging hydride liiJ'Ind. Probably the most famous bridged hydride in
ioofl.!.Uflic chemistry is diborane.
more extensively in Chapte.r 16). in
which two of the H atoms
the pair of boron atoms. UseruJ paraUcls may be
tlra"'n between t.h e hydride bridGes in borohydriLies and those in metal complexes.
The complex
is similar to [BH)- H - BH,J - in the sense
that both can be said to involve donation or u bonding pair of electrons (those in the
B-H and Cr-H bonds of (BH.I- and (HCr{COl,n to a Lewis acid (BH, or
Cr{C0l5 ] :
_.....H
L,M
_.. . H,
+ ML,-- L,M
ML
(15.32)
In molccul"r orbital terms. the donation can be view.:d as a HOMO- LUMO

tion !Chapter 9). Double hytlrido britlces. as founll in B: H,,. ;llso arc cxhii1itcLI hy
himct;lllic species such as thc chromium anion rormcLI in Eq . IS. IK. The similurioy
between these two dillfidcctl species is underscore<l by the fnctth;n their Lewis acid
an.l Lewis base fracmenrs can be interchanged: [HCriCO>,l- reacts with OHJ to
form:" '
'' Honillun. 0 . G.; Cr:>blroe, R. H. J . otm.

S<H". 191111. 1/0,
_..
P. J .; Cai, L ; t.m. 2.. : Rich>rds. R.: H:oq,cn,. J. J. A,.. CMm. S<H". tftt. IIJ.
4173-IIIW.
'' t>.thl. L F. ANI. NY Acod S..t. t91J. 115. 1-26.

"' OarmsbotJra. M. Y.; Bau. R.; Marb. M. W.: Burch. R. R., Jr.: O.::.tnn. J . C. SL11cr, S. J. Am.
- - -- --
CiJ<,m. So<-. 1912, 104. 6961-$69.
Metal Corhonyl Complexes
647
The bridging hydride interaction. whether it involves two boron atoms. two metal
atoms. or one boron and one metal atom. is best described in tenns of a three-center.
two-electron bond (see Chapter 16).
Parallels with
Nonmetal Chemistry:
lsalabaJ Fragments
Many of the reactions of metal carbonyl complexes parallel closely those of certain
nonmetal elements and compounds. For example. the Mn(C015 fragment has 17
valence electrons. one short of the total necessary to fulfill the IS-electron rule. It is
analogous to the chlorine atom and the methyl free radical. each with seven vnlence
electrons. one short of a noble gas configuration. 1be compounds and reaCtions of the
pentacarbonyl fragment may thus be reluted to similar ones for chlorine or the methyl
group. All three ure formally free rndicals and much of their chemistry derives from
pairing the odd electron: The manganese carbonyl normally e!lists as a dimer.
(cr. Cl!.
but it may be reduced to the anion.
(cf.
CH) in CHJMgXl. which is the conjugate base of nn acid.
lcf. HCI . CH 4 l:
furthermore. it will combine with other
having n single unpaired electron. for
example. R. and r. to form neutral molecules. RMn(COl. ccf. RCI . RCH,a and
MniCOl,l lcf. ICI . CHJI). The three fmgments may be
as
<'1/llictle/11 gm11psJ1 or :JS i.wlobal
The concept is an outgrtlwth of
equating the Lewis octet rule of organic and main-group chemistry with the 18electron rule of transition metal organometallic
Of course one should not
push these ideas too far. For example. pcnl:ll:arbonylhydridomanganese is a much
weaker acid than is HO. and methane normally not considered to l>e an acid :u all.
The isolobal formalism is more conc.:rnctl with structurdl prcdiclio>ns b01sed on electronic simil:1rities th:m with topics like polarity.
lsotobal frdgments have relatinn.ships that su beyond simple electron counting.
The
ek:ctron density of the
(isolobal with MntCOI,. but
simpler for cak."Uiationsl may be compared with th:ll of the methyl mdical .
Fig.
15. 1.!1. When one examines the overla p inle,;r:.ls or these two isolobal
with
rcspccl lo an incomins probe such as a hydrogen atom. the resulls ilre remarkably
15. 131. The manganese fm_!!tnCIIt :I ways has a
grc::uer overlitp.
similar 1
but the dependence on distance is csscuti<lly id.:ntical.
T:tbk 15.6 lists a numher of
or transition met:l fr:gmcnts ihm are
isnlnl-al with
fragments . Metal fragm.:nts with 16 ekctrons will behave as
(in>up VIA 1lM dements. Thu' Fc<Ct>t may form
td. H:S l :tnd
td'.
Finccn-clcctrnn
such as lrtCO o, .tre
wilh
CH mid "ith Group VA t 151 clements. such as phusphnrus. E"ch uf these i' three
electrons ,bon nf a closed shell and
has lhn:c dircctcu ori>itals which form :1
triangular face . Hence the complex
is hostrudural wit h the P, molecule
(Fig. 15.1-11
well :ts wilh telrahcdranc . ICI-11,.
Emticr in this chapter. the polynude"r c:rbonyl complex Os4 tCO>u. w:1s referred
to as an analogue of cyclobmanc. It should now be dear lhat the .:onnectiun between
o-.
, Fooo.t . A. S.: Fo<&cr. M. S.: l);lhl. 1.. F. J . Am. Clrcm . Sor. 1969. <1/,
EJ..c. t976. 5J.
Hotfm:onn. R. An)l- Chom.
/111. t;;J. fj,J!/.
F.lli>. J E. J .
t982. !I . 711-7'..4.
,.. The ioolob>l conccpl . lil<c most of Sherlock

seems uhio."'' in hmd,.;;ht . bolt
il was tnt propo<ecl in its pccscnt tOnn l>y Holf".'tn. II h.s ..;nee hc(11 ebborntecl br Dahl.
W:Kk.
Ellis. n<l ctensiYCty dc:clurcd hy HolTmann. t!kc p of Mill!,"'" " P.: Joh"'ton.
R. L. Srrmt . IJ,cdinK tlkrlint 1987. 1>/J. :9-1!7.tll w-..., Hulfcoonn' lllcOtical worl< in lhi >r<a.
much or which;, he yond the <Cope of Ihi$"'""' lh>ot rnmKd the
for his Nul>cii3UteDtc 3ddrcss
(se<: Foolnotc ll!l.
648
15 Organcmetallir: O.emistry
Fig. 15.12 Calculllled

con1our diasrams for the
i$olobalo 1 orbitllls of
[MnH,r - (left) and (CH.J.
f> .
:;.'f"
"
(riahll The coniOurs are

plotted in a plane passing
11lroua;h manganese and

lhree hydr()8en atoms and
throuGh c.orbon ond one

h)'drosen. )From
.L.
Holfmann. R.
Clrtm. Int. Ed. Enfll. 1982,

1/. 711-724. Reproduced
wich perm<s.ion.)
Fi!J. 15.13 Overlap
"'
o"
K II
IU
''
intearals for lhe in1erac1ion

between the"' frontier
omlal of [MnHJr- or
(CH,r ond a Is orbital on
H at a d$nce R from the
Mn or C. )From Hoffmann.
R. i\ng,w. Clt,m. Int. Ed.
Engl. 1981.21.711-724.
Reproduced with
permission.)
Ill AI
Tallie 15.6
Sotne isaJobal trOftsitloA

metal and moin gravp
frag-
CHt
Ni(C0)4
Fe(CO),
Cr(C0)6
CH]
Mn(CO),
Co(COJ.
Fe(C0)2Cp
CHi
Metal Carhonyl Complexes
Col
649
(b)
fi9. 15.14 Comparison ol (a) lr.CC01 11 and (b) P. Both an: teuamcn. camposed ollhe
isolobal fra&mtnls lr(CO), and P, rcspeaivdy, QCh ol which is trivalent. (Sinlclllre (a) from
Wilkes, G. R. ; DaN, L F.
ill
Chlmistry 1961, 1, 71. Reproduced with
permission.)
the two compounds goes beyond the fact that both passess a four-membered ring. The
building blocks of the two structures. CH2 and Os(C0)4 are isolobal fragments. In
fact the isostructural series has been extended tO include
which has
two 0s(C014 and two
fragments in the ring. and Os(C0) 4(CH 2h. with a ring
consisting of one 0s(C0) 4 and three CH1 units ..o Our earlier comparison of the
bridging hydrides of boron and transition metals also could have been couched in
terms of isolobality. The Lewis acids. BH 3 and Cr{CO),. are isolobal fragments. as are
BH4 and (HCr(COJ,r .
Less obvious than the above examples are isolobal relationships that exist between fragments which appear to have different numbers of frontier orbitals. The
addition or subtraction of H+ to an organic fragment does not change the number of
electrons in its frontier orbitals. As a consequence, CH 1, CH;, and CH- are isolobal
fragments. This resuh is less surprising if you consider that there are a variety of ways
in which the carbon atom may be hybridized. It is worth noting that if t wo fragmnts
are both isolobal wilh a third, they are isolobal with each other as well.
We shall encounter further examples of isolobal fl'llgments later in this and
subsequent chapters, but fClf' now we can sum up their essential features as follows:
Two fragments an isoloba/ if the number, symmetry properties. approximate tmergi.rs. and shapes of
frontier orbitals and the numbtr of electrons in them are
similar.
0 . P.: Bender. B. R.; l'bton. J. R.; Latson. A. C.; Vupmini. P. J.

1991, tO.
Undnct. E. : Jensen. R.M.; Hiller. W. ; Fawz.i, R. Clrtm. lkr. 1919. 121.
650
1S Orgonometollic Chemistry
Nitrosyl Complexes
Few complexes containing only nitrosyl ligands are well charncteriz.w. but many
mixed c:arbonyl-nitrosyl complexes are known. They may be formed readily by
replacement of carbon monoxide with nitric oxide:
Fe(CO>s + 2NO -
Fe(COMNOJ! + 3CO
(15.33)
+ 2NO -
2Co(CO))(N0l + 2CO
(15.34)
Unlike carbon monoxide. which can be used in excess at high temper.uures and
pressures, nitric oxide in excess can cause unfavorable oxidation. and at high pressures and temperatures it decomposes. Many of the current syntheses avoid the use of
nitric oxide by substituting nitrosyl chloride. nitrites. or nitrosonium salts:!
[Mn(CO),r + NOCI -
+ NO+ - (Co(C0)4r +NO;
+ 2C0z +
a- +
CO
(15.35)
+ CO
HzO
(15.36)
Co{NO)(COh + 2HCO) +CO

(15.37)
Although the nitrosyl group generally occurs as a terminal ligand, bridging nitrosyls are also known:
(15 .38)
As in the case of the corresponding carbonyl complexes. infrared stretching frequencies are diagnostic of the mode of coordination.l For the product in Eq. 15.38. v
(lermiMI NO)= 1672 cm- 1 and (bridging
ISO.S cm- 1
Since the nitrosyl cation. No. is isoelectronic with CO. it is not surprisinglh;at
tho.:re is a sreat similarity in the behavior of the two ligan.ls. They etch llave three
bon.ling pairs between the atoms and lone pairs on both atoms. Ahh<>IIJ,!h dtho.:r alum
in NO is a potential donor, the nitrogen utum coor.limllcs preferentially tcf. carhon
monoxide). avoiding a large formal positive charge on the more ele<:trunc&ativc
oxygen atom. However. in one important respect the nitrosyl !!fOUp behaves in a
manner not observed for carbon monoxide. Although most nitrosyl ligands aj)pl!ar to
be linear. consistent with .fp hybridization of the nitrogen. a few cases of .listinclly
bent
are known. A bent nitrosyl li8and is an analogue of an organic nitroso
group or the NO group in CI-N=O. where the nitrogen can be considered to be sp!
hybridized and bears a lone pair. It is this lone pair that causes lhe nitrosyl group to be
" Excc('ll for CrtNOJ no binary mclal nitrc><yl complexes have been ,Jbt:oin.-.l in run: fO<m. (j..,.t.
M. F. : Hillier, I. H.: Vincent, M.; Ro:li. M. J. Clom. SuC". Clmn. Conmmn. 1llll6,
> CaultOn. K. G . Cn<Nd. Clrtm. Rt'l'. 1975. 14. 317-JSS

oft he nitrosyl group scn.itive tu other hundins f'IC:unclCrs ml h found
over a ronae of nboul IO!l0-:!0110 em ' '. For carbunyl-nitro<yl COf11l>lcxcs. the N-0 <ttcodl ;.,
tytricaUy found belwccn ISOO and 1900 c:m .
., T)>e <!retching frequency
Nitrosyl CCMIIpleaiiS
65 1
ben!. In the neutral atom method of electron counting, a linear nitrosyl ligand is
regarded as a tllreeelectron donor and a bent nitrosyl as a one-electron donor. The
count for the linear case includes the nonbondi"G elect ron pair on nitroge,n as well as
the unpaired antibonding electron in NO:
M
+ :NEO: -
2-
M-N =:O : - M =N=Q
US.39)
In the oxidation stale method, the ligand is viewed as a coordinated nitrosyl ion. NO+.
when linear and a coordinated NO- when bent; it is a two-electron donor in both
forms.
The first well-characterized example of a bent nitrosyl ligand was that found in a
derivative of Vaska's complex:
(15.-10)
The product is square pyramidal with a bent nilrosylligand (.. lr-N-0 .. 12.r1 at
the apical position (Fig. 1.:5.1Sa)... Other complexes with a bent M-NO have been
found. including the remarkable e xample (Ru(Ph 3 Pl:(N0l:CIJ+[ PF; J. which contains
botlllinear and bent nitrosyl croups"' (Fig. IS. ISb).
The questioA of whtther a nit.r osylligand will be linear or bent re:>olvcs itself into
whetller the pair of elecuons in question will be forced to reside in an o rbital on the
nitrogen atom (bent group) or whether there is a low-lying metal-based molccular
orbital available to it. If there are available non bonding MOs on the metal (an t'lecrronpoor
the pair can reside there and allow the nitrogen 10 function as an sp u
donor with concomitant ,. back bondi"G. On the other hand. if all the low-lying
orbital:s on the metal are already tilled (:In eleclrtmrldt system!. the pair of
tot
tbl
Fig. 15.15 Complexes containina hcnt nitrosyl '"'ups: 1111 llr(PPh,J:,CCOI!NOICW and
(b) JRu(PPh:s}:(NO):CIJ+. Phenyl JII'OliPS have been umitted for clllrity: distances :.re in
picometcr'S. [Structure (nl from Hodason. 0 . J.: P3ync. N. C.; McOinncty. J. A.: Pearson. R.
G.; lbers. J. A. J . Am.
Soc. 1968. 90. 4486-1488. Structure (b) (rom Pierpont. C. G.:
Eiaenbcra. R. lniXg. Ch1m. 1972. II. t08ll-t094. Reproduced with pc:rmis.-'on.J
.., Ho<Jcson. D. J.: then. J. A. l ntw/1.
t9611. 1.
._,Pierpont. C. G.: Elscnbera. R. lnurt:. Cat..... 19n. II. 101111-ttl');l.
lllwlkll. L K.: Mif18U".

0 . M. P.: Tcw. 0 . G.: Larltwonhy. L F.: Sonddl. 8.; Povey. 0 . C.: Muson. J. J. Clwn. Soc.
Clvm. CcmMttn.
125-126
.,. This is a rdalivc term. AD mculs ifl carllonyl-nit""'ylsysocms are relatively dc<:oron nch c:omporcd
willl. ror oample. those in fluoride c:anplexes..
652
15 Org anollletallic Cloemislry
occupy an essentially nonbonding orbilal on the nitrosen. requiring trigonal

hybridiz.ation and a bent system. A comparison of the bonding possibilities for NO and
CO is shown in Fig. IS.I6.
The metal-nitrogen bond lengths in the ruthenium complex containing both types
of nitrosyl ligands (F"tg. IS. ISb) are in accord with the view just presented. ln the linear
system there is a short metal-nitrogen bond (173.8 pm) indic11ting subst11ntial .,.
bonding (as in metal carbonyls). The bent system. in contrast. shows 11 relatively long,
essentially a-only metal-nitrogen bond (185.9 pm). It would be expected that the
N-0 bond of a bent nitrosyl would be longer than that of 11 linear nitrosyl. However. the insensitivity of the NO bond length to smnll changes in bond order coupled
with systematic errors in the crystnllographic llnalysis make evaluation of such
data difficult. Within experimentnl error. the bent and linear N- 0 bonds of
[Ru(PPh:Jh(NOl:CI)+ are the same lenglh (117.0 and 116.2 pm). The N-0 bond
lengths in NO+. NO. and NO- are 106. liS, and 120 pm, respectively. We can only
conclude that the NO bond order, for both the apical and basal arrangements. lies
between two and three.
We can actually see the process of electron pair shin with a resultant change in
structun: in the complex ion
(where dian is a bidentate diarsine
ligand) (Ftg. IS. I7). The
rule predicts that the nitrosyl group will be linear
(a three-electron donor). as indeed it is. React.ion of this complex with the thiocyanate
ion (a two-electron donor) would viotate the IS-electron rule unless a pair is shifted
from a molecular orbital of largely metal character to an orbital on nitrogen. This is in
fact what happens and "stereochemical control of valence" results.7 As NO goes
from being a three-electron to a one-electron donor. a coordination site capable of
accepting a pair of electrons becomes available.
must
M- N
0
M-c.=o -
M=c=o
o=c=o
tal
Fig. 15.16 Geometry (linear vs.. bent) c{ nhrosyl lipnd$ corrclaled with the hybridization of
the nitrogen atom and parallel c:relalions for anale&ous compounds
carbonyl
lipnds.
41
Encmart. J. H. ; Fellh...,, R. D. J. Am. Clwm. Soc. 1974. 911. 5002-S004.

Encmart.
J. H.; Feltbom. R. D. O>otd. Clw'". R,.,. 1974. /J, 3}9-406. Fdlbam. R. D.; Enemarlc, J . H. In
Topia in
G. L . Ed .; Witty: New Yorlc.
1981.
F"og. 15.17 Stcn:ochcmic:al c:ontrol o( v.Knce. Note loc&liulion of t he lone pair on the
nitrOgen atom and b<ndi111 of the niuosyl troUP upon :lCiclition of tbloc:yanate ion to the
lon&ths ore in pic:Qmeters. IFrom &ematt. J . H.; Fellham. R. 0 .
c:oocdination
l't. Noll. Acod. Sci. USA.
Complexes48
1972. 69. JSlA.
with permission.!
Molecular nitrogen. N 1 , is isoelectronic wilh bolh carbon monoxide and the nitrosyl
ion but. despite the numerous complexes of CO and No. for many years it proved to
be impossible to form complexes of dinitrogen. This difference in behavior was
usually ascribed to the lack of palarity of N 1 and a resultant inability to behave as a
., acceptor.49
The first dinitrogen complex, characterized in 196S, resulted from the reduction of
commercial ruthenium trichloride (containing some Ru(IV)I by hydrazine hydrate.
The pentaammine(dinitrogen)ruthenium(ll) cation that formed could be isolated in a
variety of sults.Xl Soon other methods were found to synthesile the complex. such as
the decomposition of the pentaammineazldo complex. [Ru(NH3)sN:J1 + . and even
direct reaction with nitrogen gas:
Z:;'
+
(Ru(NH 3),H 10)1 +

-
(15.41)
(Ru(NH3),NJ1 +
(15.42)
.. Ka\JI. B. B.: Hayes. R. K.; GeorF. T. A. J . llm.
Snc. t990. Ill. 2001-2003. Birlt, R.; B..U,

H. ; Hunna. G. ; Zsolnai. L
&r. 1988. 121, ISS7-1564. Henderson, R.
G. J .;
Piclteu. C. J . /ldlt. ltiOTII. Clrtm. Ro<l<><:lwm. 1M3. 11. 197-292. PeliUn, P.: Boa. R. Coord.
Chrm. Rrv. 1984. JS. S}-112. Ldllh. 0-J . Ace. Clorm.
tm. 2.$, tn-181 . Col.....an. J. P.;
HuJcbison.. J. E.; l.opa. M. A.; Guil:lrd, R . J. lim Chm. S. 1992. /14, 8066-l!013.
., Note. hoWCYCr,thollhedipole
ofcar11on monoaMieis eatrcmdy small: O.J7S x I0- 10 C m
(0. 112 D).
,., Allen. A. 0 .; Senolf. C. V. J . CMm. Soc. Clwm. Ct>mmun.
621-622.
654
15 Orgonometaltic Chemistry
The unexpectedly strong nucleophilicity of dinilrogen shown by its displacement of

w:uer in Eq. 15.42 is also exhibited in the formation of a
complex:
(Ru(NH,)5NJ 2+ + (Ru(NH,),H2 0]2+ [Ru(NH 3),NzRu(NH 3)J]..
+ HzO
(15.43)
There are two structural possibilities for terminal dinitrogen ligands and two for
bridged cases:sl
M-N-N
M-N- N- M
end-on brid&ina
_....N...._
M,I_....M
N
Fig. 15.18 Structure o(

M01Me,J
Bood tc"'ths
in
pcomctcn. (From Y05hi<1>.

T.: -''dM:hi. T .:
M.:
T .: Hi.:u.:hi. T .
J . Am. C'IIC'm. Sm:. t 'Jl!ll.
1/0. 4l!n-ll!i 3. u,cd wiJh
pcnni$sion.)
An X-ray study of the original ruthenium-<linitrogen complex:l2 indicated lhal the

nature of t.h e Ru-N-N tinkllge was end on. but disorder in the crystal prevented
accurate determination of bond lengths. Since then, many structures of other dinitrogen complexes have been determined, including the bis(dinitrogen) crown thioether
complex shown in F'JC. 15. 18.53 The results for this complex an: typical and show that
greatly resembles CO in its bonding to metals. Back donation of electron density
from the metal into., antibonding orbitals is apparent from the short Mo-N bond.
which is more similar in length to an Mo-CO bond than to the Mo-NH 3 bond in
am mine complexes. The mean N- N bond length (ItO.7 pm) is slightly greater than
that found in molecular nitrogen (109.8 pm). suagested a weakening of the nitrogen-nitrogm triple bond from the donation of electron density into the 1r antibondiOI.!
orbitals of nitroge,n (cf. the value of 111 .6 pm for a bond order of 2.5 in N.!"). No
examples of side-on binding by N 1 have been confirmed in nonbridging
The Raman stretching frequency of free N 1 is 2331 em- . Upon coordination. this
vibration becomes infrared active and shif\s to a lower frequency . Forex01mple. strong
N-N stretching bands appear at 2105 em- for
and at 1955 and
ltl90 em - a fo r
.
It appears that the metal-ligand bonds in carbonyl and dlnilrogen complexes are
similar but somewhat weaker in the dinitrogen complexes. Carbon monoxide is not
only a beuer u donor but also a beuer "acceptor. This is 10 be expected o n the basis
of
polarity exists in the CO molecule (see Fig. 5. 18) alkl the fnct that the 1r
anlibonding orbital is concentrated on the carbon atom (see Frg. S.!n). which favors
overtap with the metal orbital. The superior ., accepting ability of CO also accounts
for the instability of carbonyl dinitrogen complexes. Both Cr(C0)5 N 2 and ds-
" Cbau . J.: D;lworth. 1. R. : Ricbards. R. L. Cit.,. Rno. lnl. 11. 5119-62S.
n Botl<>mlcy. F.: Nybu<g. S. C. Acta V,stollotfr. Stet. B 1961. U. t:!ll'l- 1293.
n Yosllilla... T.: Adad!i. T. : Kaminab. M.: Ucda, T .:
T. J . Am. Ch<'m. S. 19118. 110.
4872-4873.
S<
Ahhoop lbere have been no sideooll stnletuta verilled by

aNllysio. r:MI1y aood spc:ctroscopic
evidence S4JR10<1s thai mode o( ccwdin81ion in (t,S.C,H,hb lctiiSiMcJhl(N.J. Jefray. J.: Loppert. M. F.; Riley. P. I. J. OrJ/altOmtt. CNm. 1m. Ill. l.S-36.
Metol All.yls, Carbenes, Carbrus, ancf Carbides
655
Fig. 15.19 Structure or

Sml'I'.C, Me,):(N,). [From
Evans. W. J.; Ulibarri,
T. A.; Ziller. J. W. J. Am.
Soc. 1988, 1/0,
6877-6879. Used with
permission.)
have been investigated at low lemperotures, but decompose when

Replacing some of the c:u bonyls with phosphines can provide sufficient
electron density to
e nhance s tability ; hence. MO(C0)3(PCy3hN 2 COin be
isolated at room temperoture.S.
( JS.U)
When dinitrogen functions as a bridging ligand. it usually exhibits end-on coonlination: this is the case in the t.liruthenium complex of Eq. IS.43. for example. Bridging
sit.le-on c:umplexes are also known. however,
D recently reponed example is also
tho: lir.st dinitrogen complex of anfekment (Fie. IS . !9).S7 In this samarium complex,
obtained from the reaction or Sm<C,Mc,t. a nt.l N., the two salll:lrium atoms and the
two nitrogen atoms a re in :t planar
The Sm-N bond distances suggest
the presence or Smt lll l. implyin& a retlucet.l N-N bontl. but strongely enough the
N- N hunt.l distance I 108.1! pm) is even shorter than that found in free dinitrogen.
The at>ility to synthesize coml'lcxes containing dinitrogen. espec ially those with
consit.lerable alteration uf the electronic s t:tte uf nitrogen. opens u p possibilities of
d irect li:\<Uion of nitrogen from the atmosphere. a long-standing challenge to the
chemist .<u alo provic.les
into the closely rela tet.l process o f biological fixation
of nitrogen ant.l thc e nzyme: s ystems in vnlvcJ
Chapter
Metal Alkyls,___
Carbenes,
Carbynes, and
Carbides
S in{:l<!. dmthlc. ;mt.l triple lxmt.ls t>ctwccn c arlxln and nonmeta ls s uch as carbon.
nitrogen. :md o xygen have long o.:cupict.l a cen tral
in organic chemistry. The
chemistry of
single bonds in main t:roup compounds (e.g., Grignard
reagents anti organomen:ury compounds) dates back to the 19th century. Transition
metal compount.l.s containing me!Jll-curhon sins lc . double , a nd triple bont.ls have come
to be unt.lerstood much more recently:
Alkyl Complexes
M-CR3
M=CR1
Although t here are some eorly e xamples of complexes in which M-C si11(!1e
bonds arc present Ie .g., {Me 3 Pt1J.
in 1907), the prevailing view for many
UpnlilCis. R. K .: Poliolco/T. M.; Turner. J. J . J. Am. Clwm. S. 1986.
"'W:oucl'fni>A. H. J.; Kuha>. G. J.: Rynn, R. R. J. Am.
S. 1!1114.
22114-:!lOt.
n Evans. W. J.: Uliboni, T . A.:
J. W. J. Jim. ('/""' S.J<'. t9111. 110. 61171-6819.
,. Cutquhoun. H. M. An'. Clrtlff.
t934. 17. 2}-lll. (l<,Ufie, T. A.: Tisdale, R. C. lMTfl. Orm.
1988. 17. 2909-2912. See
ll rur
or N 2 to NH,.
J>
65 6
years was lhal lransJUon melal 3lkyls. unlike the main group alkyls. are lher
modynamic:ally unslablc . This conclusion was reached because synlhelic altempts 10
oblain compounds such as diclhyliron or diclhylcoball (e.g. by reac1ions be1ween
FeBr, and EtMgBr) were unsuccessful. In fact lrnnsilion metal-carbon bonds are in
gcne.:a. no less strong than main group melal-carbon bonds (Table 15.7). However. it
should be noted that. allhouJ!)l metal-carbon bonds decrease in slrcngth as the atomic
number increases for the main group metals. they increase in strength as the atomic
number increases for transition metals. Thus the early focus o n the lint-row transition
series was least favorable from a thermodynamic point of view. However. the principal difficulty in obtaining transition
bonds was not thermodynamic but
kine1ic. There arc a number of favorable palhways available 10 mc1al alkyls for
decofl\POsition. One of the most important is p elimination (page 699):
H
CH 1
M- Il
M +
(15.45)
/'\.
R
H
A great deal or synlhetic success has been achieved by using alkyl groups that do no1
have p hydrogen atoms. Among lhese are PhCH1 Me, and CH1 CMe,, none of which
can decompose by f3 elimination.
Table 15.7
Bond clnociafion
enthalpies, 0, lor
onetakarl>an bonds
O,ltJ
Complcxb
ThCp,Mc
Ti(CH1 CMc1) 4
ZI{CH1CMe,)4
Hf(CH2CMe,)4
TaMe,
WMe6
351
198
249
266
261
160
Co(dmg)1(PPh3)(CH1 Ph) 108
Mn(C0)5Mc
Re(CO),Mc
cirPt(PEt.J:tMCz
187
220
269
Bond
C-C
Si-C
Ge-C
Sn-C
Pb-C
358
311
249
217
52
onor 1
Metol
Carbenes, Corbynn, and Carbides
657
The syntheses of lnlnsition metal alkyls can be accomplished in several ways. A

common approach is to take advantace of the nucteophilicity of a carbonylate
For example:
[Mn(CO)s]- +Mel -
(15.46)
MeMn(CO), + 1-
In this reaction [Mn(CO>,r. which is quite nucleophilic, increases its metal coordination number by one. The reaction may be viewed as an electrophilic attack by R .. on
the metal. Similarly, it is possible to prepare bridging alkyl complexes by this
method:60
+ CH 212
,.,c,
IOCJ4 Fe- -Fe(C0)4 + 21-
(15.47)
A second approach involves a nucleophilic auack o n the metal. This is seen in the
reaction of methyl lithium with tungsten( VI) chloride:
+ 6MeLi -
WMe6 + 6Li0
(15.48)
Tile red crystals which form in this reaction melt at 30 -c and arc reasonably stable.
TWo other important routes to transition metal alkyls arc oxidative addition and
insertion, topics that are discussed more in the section on organometallic reactions.
Corbene, Corbyne,
ond Corbide
Complexes
It has been relatively recent In chemical chronology that compounds containing fonnal
metal-carbon do uble and triple bonds were discovered:
MaC- R
The first of these are called c:art>ene complexes and the Iauer are referred to as
carbyne complexes.61 The first carbene complex was reported in 1964 by FISChe,r and
Maasb<ll6l and was prepared by reaction of hexacarbonyltungsten with methyl or
phenyl lithium to generate an acyl anion which was then alkylnted with diazomethane.
W(C0)6 + RLi--+ [W(COJ,!CORWU"'"
CH,t<.
(OC),W= C/ R
'-oMe
(15.49)
S9
Nucleophilicity it a kinetic term used to cl..cribe the rtltc 81 which a nuc!coptilc re.tcts with a
sut>.traJc. Relative
oC [RcCCOisl- . (Mn(CO)sl-. anciiCo(COM- as mcasurccl b
t heir reaction with Mel are 22.900. 169. ;and I. respectively. Peanon. R. G.; Fclore, P. E. J. Am.
Soc. 1980. 101, tS41-IS47.

C. E. Jr.; Riley, P. E.: D>vis. R. E. ; Pettit, R. J .4m.
S oc. t9110. /01, 17S2-17S4.
Holton. J.; Lippert, M. F.; Pwtt, R.; YOrTow, P. I. W. Clwm.
1913, 6J, llS-201
., Catl)enc complexes- also rcremdiO in Ihe lterallft as . .ylidenes and cart>ync CO<nJ1cxes arc
somerimes calle<l alcyliclynu.
60 Summer,
t: FI>Cher, E. G.;
Ma.ub61, A. ""'""
lnl. EJ. &6f. IH4. J, 580-581.
Sub!ilantial improvement in the convenience and scope of carbc:ne synthesis followed

by replacing diazomethane with other alkylating agents such as R)osF; or
Mc:OS01F.63 (See Eqs. 15. 148-150 for synthesis from [Cr(C0l,J2 -. ) Hundreds of
cartc:ne complexes or the type shown in Eq. IS.49 are known. They are characterized
by having a metal in a low oxidation state. 7t'acceptin& auxilliary ligands, and subst._
tuents on the cartc:ne carbon capable of donating .,. electron density. When they
participate in reactions. the carbc:ne carbon behaves as an electrophile. Complexes
having these properties are known as "Fischer" cnrbenes.M The
of these
complexes in organic synthesis is presently under intense investigntion (see
page 70S)."'
Free cartc:nes exist in both triplet and singlet states but those containing a
heteroatom (e.g., 0 or N). as found in Fischer carbenes, tend to be of the latter
variety. Thus the free ligand may be represented as follows:
The pair orelectrons in the sp2 Ol'bilal may be donated to a metal to form a cr bond. :uxl
an empty p. orbital is present to accept .,. electron density. Filled d orbilals ci the
metal may d"Onate electrons to the p, orbital. to give a metal-carbon double bond. and
electrons from filled p orbitals of the oxygen :uom may alSo be llonated to form a
c.>.rbon-oxygen double bond
15.20). Resonance form IS .2llb appears to be
dominant and, although the M-e bond is shorter than expecletl fora single bond. it is
too long for an M-C double bond, leadin& to the conclusion that the bond ordc.r is
between one and two.
Just ten years after the discovery or FISCher's eleclrophilic camene. Schrock
discovered a class of carbenes which are nucleophilic.M
These nucleophilic carbc:nes are composed or early transition mo:tals in high oxidation
states. nonI'T accepting auxilliary lisa ntis. and nonI'T donatio&
on carbon.
N,,..
Mcthylfluorosui(Cirl;lte is a
and very 1olc :alkyl!\llnaoaenl. Sec Otlff.
176. j-1
(]61. s.
"' They arc calletl carbo<""" even thoutll> they wc not rmdc fn1ftl corhcno< and
arc nol
synthcsiud from them. Sec Dol%. K. H.: FiKher. E. 0 .: Hofnllilln. P.:
F. R.: S.:hllboert.
U. : Wci<s, K. Ttclto.ritmn MrtGI Crulwt"' Cu,..,,rxt.: Vcti:;J Chemic: Oo:erfic:ld l!c:M:b, FL t'I!G.
"'0<\tz. K. H.
Clltnt. Int. J. E.tiJ:I. 1911-1. lJ. 5111-608. Qaj<cy, C. P. In TruMitirm lolttlli
O.""''"'""DIIitr ;,. Or,uw SyntltrJiJ: Alp:r. H.. Ed.: Act<L-mic: New Yclfic. l'nl\: ChaJ'llcr 1.
Wulff. W. 0 . In
In
Clr.omitrv; Liebcsltino.l. L S.. Ed.: JAI; Gra:nwich.
19117; Vol I.
""Schrodt. R. R. J. A.m. C1ttm.
96, 6796-4>797.
Metal Allcyls, Carbenes, Corbynes, oad Carbides
659
/OP.
M=C
'
lb l
Fig. 15.20 ResOnance forms for a 1ransi1ion metal c:arbene complex. Form (n) shows
rnetal-cartx>n double hond character Which results from donation o>f metal d electron densily
lo an empty p orbi1a l or carbon. Form (b) shows oxygen-carbon double bQnd
which
results from dunntion of oxygen p eleCtron density 10 an empty p orbiw or carhon. Form (b)
provides lhe dominaru contribution.
They are called "Schrock" corbcnes to dislinguish t hem from the Fischer carbenes.
One
10 view these complexes is in 1erms of two orbitals on the carbene. each
housing an unpaired elecrron
slate) overlapping wilh rwo met.al orbilals. each
of which provides an
_ _,..II
M-C
'H
(15.51)
The clcctrophilic nature of a Fischer carbenc is illustr.ued in t he following

re:.tclion:
,.,....0.\Jc
COC>,Crc,
(15.5.!)
Me
In thi.s reaclion the nudel)phile. NH,, attacks the carbene carbon to form an interwhich eliminates methanol. The reaction is favorable because nitrogen is not
as electronegative as oxygen and its ., donating ability exceeds that of oxygen
[stabilizing resonance form (b) in Fig.
The nucleophilic nature of a Schrock cart>ene is seen in its reaction with Me3AI:
Taylor. T. E.: Hall. M. B. J . Am. Chm. S11c. 1984, 106, 1.576-1384.
6GO
IS Chgaeometallic Chemistry
In many of their reactions, these carbenes behave like the familiar Wittig reagent,
Pll3 PCH2 Schrock carbenes are important intermediates in olefin metathesis.68
Classificat.ion of cartlene complexes as Fischer or Schrock perhaps focuses too
much on their differences and too little on their similarities. Both contain a metlllcarbon bond of order greater than one. Whether the cartlene carbon tends to seek or
provide electrons will depend on the extent of v bonding involving the melal and the
carbon substituents. Some carbene complexes lie between the Fischer/Schrock extremes, behaving in some reactions as nucleophiles and in others as electrophiles.69
A decade after the announcement of the metal-carbon double bond, Fischer's
group reported the first complex containing a metal-cartlon triple bond.70
CI(OC)4 W==CMe
(15.54)
The cartlyne ligand may be viewed as a three-electron donor, similar to the nitrosyl
ligand, with a pair of electrons in an sp orbital and a single electron in a p ortlital.
Donation of the sp electrons and pairing the p electron with one from the metal atom
gives au bond and a v bond, respectively. The second v bond results from donation of
an electron pair from the metal atom to the empty p ortlital of the ligand.
(lS.SS)
Shortly after the preparation of the first cartlyne, Schrock's group provided a high
oxidation state comptement.71
(JS.S6)
It also proved possible to put alkyl, carbene, and carbyne ligands into the same
mofecule.n
.. Schrock, R. R.
1983, 219, 13-18.
"'Gallop, M. A.; ROper, W. R. Ad.
Chem. 1986, 25, t21-198.
., Fis<:her, E. 0 .; Schubert. U. J. Orgon011WI. Chem. 1915, 100, S9-8t.
11 Clut, D. N.; Schrock, R. R. J. Am.
Soc. 1978, /00, 6n4-6n6. Schroclc, R. R. Ace. Chem.
Rn. 1986. /9, 342-348.
n Churchill, M . R.; Younss. W. J. lnort. Ckm. 19'79, /8, 24S4-24S8.
Metal All<yla, Corloenea, Corbynes, and
661
The tungsten-carbon single. double. and triple bond lengths in this compound are
225.8. 194.2. and 178..5 pm. respectively. and the nccompanying w-e-e bond
angles nre 124. tso. and 175. nU of which is quite consistent with tungsten-carbon
bond orders of I. 2. and 3.
Systemntically removing hydrogen atoms from a methane molecule would leave
us with a carbon atom in the final step.
-H
CH -
-H
eHJ - . .
- H
-H
(15.57)
We have thus fnr seen complexes containing alkyl. carbene, an<.l carbyne ligands. and
if you hnve speculated llbout the possibility of atomic ca.rbon functioning as a ligand,
your thoughts have been well plnced. Complexes in which carbon is bound only to
mel:ll atoms are known as Clllbido complexes (Fig. 15.21). The first example was
reported in 1962, before carbene and carbyne complexes were discovered. but until
recent.ly , carbido complexes remained chemical oddities synthesized by a variety of
5C"endipitous routes.n A ca.rbon atom surrounded by metal atoms is not very reactive, but if it can be exposed by removal of one or more metal atoms, it becomes a
reactive species. Oxidation of(Fe6C(e0) 11
(Eq. 15.185) removes two iron atoms as
Fe2 ... and uncovers a positively charged carbon atom which can react with nucleophiles such as carbon monoxide (see Eq . 1.5. 186). In effeet, this sequence creates a
carbon-carbon bond. which is always of Interest to the organic chemist. and furthermore the added carbon can be easily functionaliza:d. Thus carbido complexes show
potential in organic synthesis.
i-
Fig. 15.21 Structural cumpiH of c:arbido complexes: (at Fe,(CO),,C. (b) [Fe,(COl,.cf- .
and (c) [Au.(PPtl,),cf. [From Brayc. E. H.; O&hl. L. F. ; Hubd. W.; Wampler. 0 . L.
J. Am. Chmo. Soc. t962. 84. 46))-4639 (a): Bradley. J. S. A.dv. Orgonom,.
1983. ZZ.
1-58 (b); Scherbaum. F.; Grohmann, A. ; Huber. 8 .; Knq:er. C.; Schmidbaur. H. Angt'lv.
lnr. Ed. Engl. t988, 21, 1544-IS46 (c). Used with permission .)
Pl'hJ
11
fb i
,.,
'' Bruyc. E. H.: Dahl. L. F.: HObcl. W.; W-plcr. D. L. J. Am. Clwnt. S.l<'. 1962. 84. 46))-46)9.
Brudley. J . S. Ad. Orgtm<>nwt. CJrtm. 191J. 12. 1-$8. Hriljac. J . A.: Hoi!. E. M.;
0 . F.
' ""'8
1.917. 26. 294}.296. Hayw.ord. CM. T .: Shapley, J. R. ; ClwKhill. M. R. ; Bueno. C.;
RhOnsold. A. R. J . Am. Clwm. Soc. 1911. 104.7347-1349.
662
1 S 0'1!an0ftlelollic O.emistry
No naromatic
Alkene and Alkyne
Complexes
Complexes between metal salls and alkenes have been known since 1827 but they
were not understood untU the Iauer half of this century. For example, Zeise isolated
stable yellow crystals after reftuxing an alcoholic solution of platinum tetrachloride.7A
Zeise's salt is now made from K!PtCI4 and C!H4 :
Alkene Complexes
(15.58)
Si.lver ions form similar alkene complexes which are soluble in aqueous solution and
may be used to effect the separation of unsaturated hydrocarbons from alkanes.
Catalysts for the polymerization of alkenes also form metal-alkene complexes which
lead to polyrneriled product.
A structural investigation of the anion in Zelse's salt has shown that the ethylene
occupies the fourth coordination site of the square planar complex wth the C-C axis
perpendicular to the plati num-liJ:and plane (Fig. 1!5.22)." Relative to free ethylene,
the
bond is lengthened slightly (from 133.7 pm to 137.5 pm). and the hydrogens
are slightly tilted back from a planar armngement.
The bond between the ethylene molecule and the metal ion may be considered as
a dative u bond to an available orbital on the metal. The bonding scheme (sometimes
called the Dewar--Chatt-Duncanson model) is analogous to that in carbon monoxide
complexes in which there is a ligand-to-metal u donation and a reciprocal metal.toligand ,. donation (Fig. 15.23). The extent of back bonding varies depending on the
metal, the substituents on ethylene. and the other ligands on the metal. For example.
in the complexes of t.h e type LRh(C,H4 )(C!FA) (where L acetylacetonate or cyclopenladienyl). the tetraltuoroethylene molecule bonds mOC"e slrong.Jy and at a shoner
distance (Rh-C = 201-202 pm) than does the unsubstituted ethylene (Rh -C =
2 17-219 pm).7f>This indicates that the ,.accepling ability of the alkene ligand !C!F4 >
<;HJ significantly influences 1he metal- carbon bonds in these compounds. As wi1h
carbon monoxide, usually only metal atoms in low oxidation states are sufficienlly
good rr donors to stabilize alkene complexes.
In extreme cases. such as Pt(Ph3 P)2(CH1 - CH2) in which the metal is very
electron rich, ,. back donation is significant and as a result, 1he carbon-carbon bond
lengthens considerably (to 143 pm) and the hydrogen 111oms are hcnt considerably oul
of lho: plane:
c- c
F;g, 15.22 The structure of
the anion of Zcise's sail.

trichloro(ethylenc:)platinate
(II) ion .
0 t/H
!
Cl
\ \ .
In this molecule ethylene lies in the same plane as the other ligands, unlike the case in
Zeise's salt where planarity is sterically prevented. By analogy to a three-membered
ring of carbon aloms, this compound may be viewed as a metallacyclopropane.
or
H H
,. F.:. a lr:mslolioD
Zeise's
papc:r. ICC Ouuics
Cutlrtlinulimo Clwmistry: P..n 1:
KauiTman. G .. Ed.: Ooocr. New Yort. 1\176; pp !1- )7.
.,
R. A .; Koctzlc, T. F.: Wiliams.. G. J. 8 .; Ar>llrews.. L C.: D:IU, 1!. lnw-,:. Clwm. lf7S. lol,
26Sl-2657.
L J.; Cramer. R. J. Am. Clo.-m. Sue.
0. R. Chrm.
tm. !U, )779-)7116.
J. A.; Rlls5dl.
Nonaromatic Alkene and Alltyne Complexes
663
Fig. 15.23 Represenlntion

of ., coordination of oo
ethylene ligand and a
transition metal.
suggesting that we can consider the two bonding extremes. w donation and metallacycle. as resonance structures:
X,, /X
M-Il
"x
x/
,...c
M,J
(3)
C,
\ 'X
X
(b)
A similar and even more extreme case of bond

is found in complexes of
C!<CNl4 in which the w accepting ability of the alkene is enhanced by its ek..:tronegative substituents. Electron-rich metals and strongly
alkene
subSiituents favor structure (b) while opposite conditions favor structure ta). Structure (b) suggests that the metal has been formally oxidized witl1 the loss of two
ligand binds to
electrons. For further insight into the mode by which the
metals. it is interesting to compare the structure of tetr:.cyanoethy(ene oxide with that
of a tclmcyanocthylcnc nickel complcx.77
L.,_
_... L
Ni
1\
Ill
12t
Both the C-C bond lengths ((I) = 149.7 pm; (2) = 147.6 pmJ and the bending of the
subslituents out of the plane [Ill = 32.2"; (2) = 38.4) are nearly the same. Although
we can draw an alternative resonance form for the nickel complex. the bonding model
shown is lhe mr/y one applicable to the oxitle. In view of the strong structur,ll
similarities . we c-.m feel justified in using the cyclic structure as an approximnlion for
ccr1ain complexes as well.
When a ligand is bound to a metal.
chemistry typically changes. For alkenes
I he ch:mge is par1iculariy dramatic. Free alko:nes are susceptible to electrophilic attack
n Mnllhcw.. D. A.: Swanson.
S'HS-S9S3.
J.: Mudlcr. M. H.: Stucky. G. D. J.
Am. ChNn. S<H:.
t971.
9J.
664
IS Orgonometabic Chmis!Ty
but not to nucleophilic attack. When coordinated to a metal. the carbon atoms become
somewhat more positive and a revenal of reactivity occ:un, i.e . the alkene becomes
susceptible to nucleophilic attack and loses its susceptibility to electrophi!ic auack.78
Alkyne Complexes
The chemistry of alkyne complexes is somewhat more complicated than that of alkene
complexes because of the greater possibilities for ., bonding by alkynes and the
tendency of some of the complexes to act as intermediates in the formation of o ther
organometallic compounds.
The simplest alkyne complexes, the metal acetylenes. resemble those of ethylene.
For example, there nrc analogues of Zeise's salt in which an acetylene molecule is
bound to platinum( II) and occupies a position like that of ethylene in Zeise's salt. In
addition. there are L.,Pt(RC...,CR) complexes that have structures paralleling th;u of
L1 Pt(H2C=CH2) (flg. !5.24). For both of these Pt(O) complexes, an approximate
square planar nrrangeme,n t around the meta.! is found. Alkynes are more electronegative than alkenes and are therefore beuer ., acceptors. Thus it is appropriate 10
view them as metallacyclopropenes:n
'\ I
C=C/
M
Alkynes have two ., and two 11'" orbitals that can polentially interact with metal
orbitals. and in some instances, it is thought !hat all of these are involved at the same
time in a mononuclear complex. An extended HOcker calculation on Mo{mesotetra-p-tolylporphyrin)(HC.sCH) supports this view (Fig. !.5.25).110 Thus both bonding orbitals of the alkyne (b 1 and a 1) can donate electron density to molybdenum to
form the l b 1 and la 1 MOs. and both antibonding orbitals
and a!l can accept
electron density to form the ib2 and la2 MOs. Notice that both 1r bonding orbitals (a 1
and b 1) of acetylene interact significantly with metal d orbitals of the same symmetry.
D"Ptl
!:!8
:
I
'06
R! p
J
pic:omccers. (From
!'\.
[__.}Ptt
i
(triphenytphospltine)diphenylacetyleneplati
num(O); bond lcnaths are in
Glanville , J. 0 .; Stewart.
J. M.; Orim. S. 0 . J.
102"
201

struc:ture of bis-
Orrarocmtl. Chtm. 1961, 7,

P9-P!O. Reproduced with
permi53ion.I
"' For afurthttdiscussionofltlisrevc:nal andod>cn(rcfernd to as

secCnblree. R. H.
1M 0fRGttOm<tollic CMmU1'7 o{ IM Transition M.,alr. Wolcy. New Yoric, 1988; p 91.
79 Cotton. P. A.;
M. /norr. Chtm. !m.19. 508-SI4.
., Tatsumi, K.; Holfmann. R.; Templeton, J. 1..- /ft01i. C,m. 1912.11. 466-468.
Nonaromatic Allrefte and Alkyne Compl
665
Both pairs of tr electrons in an alkyne ligand are more likely to be involved in the
bonding if it is coordinated to two metal atoms. If acetylene is allowed to react with
dicobaltoctacarbonyl, two moles of carbon monoxide are eliminated;
(15.59)
The production of two moles of carbon monoxide and the IS-electron rule lead us to
predict that the acetylene molecule is acting as a four-electron donor. In fact this is
just one of many complexes in which alkynes bind in this fashion.8t For example, the
structure of the diphenylacetylene complex in Fig. 15.26 shows that the positions of
the two rhodium atoms are such as to allow overlap with both ., orbitals in the
carbon-carbon triple bond.82 The extent of back donation into the antibondfng orbitals
determines the lengthening of the C-C bond and the extent to which the C-H bonds
are bent away from the complex. Bond length values vary greatly from system to
Railhby, P. R.; Rosales. M. J. Mv. /norg. Radiochtm. 1985, 29, 169-247. Rqct". D. L : Huff.
M. F. ; Wolfe. T. A.; Adams. R. D. OrganometaRio 1989, 8, 848-8.50.
n Ben-y, D. H.; Eisenbc.-J. R. Organumttallic:s 1981,6, 1196-tSOS.

strucrun of
Rh:(CO)z(PJ>h.CHzPI'Il!ll
(PhCc CPh). All but one
carbon atom of each phenyl
arou.p on lhe piMphine
liaands have been omilled

for clarity. (From Berry,
D. H.; Eisenbera, R.
1987. 6,
wiJh permission.(
system,SJ but for the rflodium complex of Fig. 15.26,the C- C bond length of 1.329 A.
indic:lles it is best described as a double bond.
Allylond
Pentodienyl
Complexes
Few licancls are as convnon and imponant to organometallic chemistry as the allyl
ICJH,l group. A recent orpnometallics text devotes an entire chapter to the use of its
complexes in organic
h can function as a one-electron donor (monohaptol
or as a three-electron donor (trihapto).
H
H!C \ /CH 2
H
-
H 2C'-
H
CH 2 a CH 2 .
CH 2
The trihaJl(o arrangement. which is by far the mo:< common. usu:1lly h;s
C-C
bnnd lcnl(lhs in accord with deiOQiization over t he three ... orbitals. The lhn!<! MOs of
I he allyl radical (Fig. 15.27) can overlap with u nml.,. orbitals of the met:al. but the OT
inleraction of the ligand with the metal
orbital is not very significant.
A variety of preparations for these complexes have been developed. one of which
is the reaction of allyl bromide with an oraanometalllc: nnion:
Na[Mn(CO)J + CH 2 =CHCH2 Br -
(CO),Mo('I 1-C3 H,) + NaBr (15.601

(15.61)
10 Gcnasio. G.:
Rossetti, R.; SIIIIIShclini. P. L. 0r,tDIVI,.,toJIN:s 1985. 4. 1612-1619.
... Collman. J. P.: Hqccl>s, L S .; Notton. J. R.; Finke. R. G. l'rirrci{ll#s and Applirotions of
Or,:unutriiiUition Mnal CMmistry, 2nd ed.; UniYcnily Science lkx>ks:
Valley, CA. 1987:
Mi.
Nonaromatic Alhne and Al.yne Complexes
667
Fig. 15.27 Diav.un sllowin& interactions belween metal d otblt:lls 1111<1 the " orbil&ls of an
ollyl li:1nd.
.,...
-.
II
..
II
H-;-H
H
Fig. 15.28 Moleculnr
structun: or
as
by nt.turon
ditrn>ction. (From Goddard.
R.; KrO,er. C.; Marie . F.;
SumAeld. R.; Zflanc. X.

Ottott<Jtn,allics 1915. 4.
li:IS-290. Reproduced with
permiosion. I
The tina reaction takes place a l amhicnt

a ncJ the second occurs when the
system is heated. Initial formation of !he monohapo complex is bc.lievecJ to be typical,
but often this intermediate is not observed .
A second syruhetic approach is to u..e a Grigt13rd reagent and a metul halide:
(15.62)
Th.: hislr(allyllnick.:l c11mph:x is u yellow . pyrophoric compound thai mchs al I "C.

lis srruc111re. \1-hi.:h
hc.:n dclcrmioiCJ hy IIClllrtln tlill"r.lctitl'l.
some of the
imptrlanl fealtlrcs uf 1hcsc .:nmrlcllcs
The lwo terminal c;u1>0n atoms
:m: furlher from the metal
pmlllmn is the: ccnlr:11 carbon atom tl'll!.O pm).
Even so. thc terminal c:orbon atoms
tiltctl townrd the mclal to provide beller ,.
overlap. The C-C-C boml al'll!k is 12o.s
mean C-C bontllength Is IH .6
pm. all of which i:; in ;tgrccm.:nt wilh a cor\iugutc:J ,. syslc:m . The anti
to meso)
hydrogen atoms arc bent
from the
anti the syn leis to meso) anti meso
hydrogen atoms are bent toward the metal .
In acJcJition lo the stereochemistry possible for allyl complexes as a resolt of
different syn und anti subsliluents. seomelrical isomers are known which arise be
atom relative to other ligancJs. Both
cause ur I he position of the ccntrnl ullyl
t'.w- anti
have been isohtted (Fis. 15.29).""
"-' <Mkbnl. R.:

C.: Mal'k. F.: 51":11\\ftckl. K.: lJr.>o1a. X. OrtnHUMrtuJiics t9SS. 4, :!115-!90.
.. Hsu. L-Y. ; Nortlman. C. E.; GibJOn. D. H.; HI<U. W L. O.,:uiHJifltltlllit:s t9H9.11. 241-2+4.
668
150rganometallic Chemistry
( Q)
Fig. 15.29 Struc:tures of (a) mdc- and (b)

Nordman, C. E .; Gibson. D . H.; Hsu. W-L
with permission.)
(b)
[From Hsu, LY.;

1989.8. 241-244. Reproduced
The allyl group can be extended to create a pentadienyl group, a five-(;arbon

system with two double bonds, CH2=CHCH =CH-CH2 . Its many modes of bonding (rl, f13 , '11) have led to a rich chemistry, including the synthesis of metallabenzene
complexes which are thought to be aromatic (Fig. I.S.30).'11
fig. 15.30 Square pyramidal structure oftris(tridhylphosphineH2.5-dimethylpcntadienyl)iridium. The six-membered rina is nearly planar and the
distances
(137-140 pm) arc consi$tent with extensive dc.locaU:zal.ion. The complex is an example of a
mctailabenzcnc. (From Blecke, J. R.; Xie. Y-F. ; Pcng, W-1. ; Chians. M . J. Am. ChC'm. Snc.
1989, Ill. 4118-4120. Reproduced with permission.(
WI
Ernst. R. D. Struct. Bonding

1984,37. 1-Sl. Blcekc. J. R.; Xic:, Y-F. ; Ptlll!, W-J.; Chiang.
M. J. Am. Clwm. Soc. 1989, Ill , 4118-4120. Blceke, J. R. AC'C'.
1991,24,271-277.
Metallocenn
Metallocenes
669
Organometallic chemistry leaped forward in t.he early 19SOs when the structure of
ferrocene, Fe(l)3..C5H,h. was elucidated."" Prior to that, ideas regarding metalligand interactions included only the coordinate covalent bond (e.g., M-COJ and I he
covalent bond (e.g., M- CH1 ) . h was revolutionary in bonding theory to propose a
metal-ligand bond between a metal and t he ,. orbitals of C,H_,. Ferrocene was t he first
d many complexes which came to be known ns mctallocenes, a name which arose
because they participated in reactions similar to those of aromatic molecules. For
obvious reasons complexes in which a metal atom was found between two parallel
carbocyclic rings became known as "sandwich" compounds. Some of these are
shown in Fig. 15.31. All of the complexes in Fig. 15.3 1, except the last two. obey
the IS-electron rule. Depending on the electron cou nting method adopted . the cyclopentadienylligand may be viewed as either a five-electron donor (neu tral atom) or a
six-electron donor (oxidation state) (Table 15. 11.
The IS-electron rule is not obeyed as consistently by these types of orpnometallic compounds as by the carbonyl and nitrosyl complexes and their derivatives.
For example. in addition to ferrocene, M(l)3..C5 H,)1 compounds are known for most of
the otherelementsoft.h e first transition series (M '" V, Cr. Mn. Co, Nil and these cannot obey the IS-electron rule. However, only ferrocene shows exceptional thermal
stability (stable to 500 oC) and is not oxidized by air. Furthermore, cobaltocene.
a
species, is readily oxidized to t he IS-electron cobaltocenium ion,
which reflects much of the thermal stability of ferrocene. Mixed
cyclopentadienyl carbonyl complexes are common: [(l)'C,H,JV(CO)J. [(,S..C,H,)Cr(COJ,b.
((l)5-C,H,JMn(COJ 3).
and
or interest is the fact that among these compounds. the oddatomic-number elements (V, Mn, and Col form monomers and the even-atomicnumber elements (Cr. Fe. and Nil form dimers, which is in direct contrast to the
behavior shown by the simple carbonyl complexes. Cyclopentadienyl derivatives are
now known for every main group and lransilion metal of the periodic table and for
most of the fblock metals.89
F'og. 15.31 Some

eishtmembered rifl&s.
or known metallocenes containlnc four-, five-, six, seven , and
Wilkinson. G .; Rosmblum. M.; Whiting. M. C.: Woodwonl. R. B. J . Am. CMm. $. t9S2. 74.
212S-2126. . 0 . Fosdler and G. Wilkinson n:;ived the Nobel priz.c in 1973 for wed done
indq>cndmtly on mculloccncs.. For a pcrSOMI ao::ccunt d Wolkiruon'a early wed. see
J. Orgonom.rt.
l!nS, 100. 213-218.
e Marl<s,
B. E. ; Striltmancr, R. J.
Clr1m. 1979, 2.S.l23-lll. Poli, R.

Rv. l 991 . 91,S09-SSI. Bunaen.
Cl.,m. 1111. &/.
1991, )(), 1069-tOSS.
670
15 Organometnllic Chemistry
Molecular Orbita ls
of Metallacenes
The imp<Jc"tance of metallocenes and the complexity of their bonding make it wortbwhile to describe them with molecular orbital theory . The properties of the molecular
orbitals of the 1r system of cyclic polyenes may be brieOy summarized as follows.90
There is a single ortital at lowest energy that consists of an unbroken, i.e., nodeless9t
''doughnut" of electron density above and below the plane of the ring . At slightly
higher energy there is a doubly degenerate set of orbitals each of which has one nodal
plane containing the principal axis. This is followed by another doubly degenerate set
with '"'" nodal planes and yet higher energy. This pall ern c{)ntinues with doubly
degenerate orbitals of increasing energy and incrensing number of nodal planes until
the number mmolecular orbitals is equal to the number of atomic p orbitals. i.e . the
number of carbons in the ring. If this number is odd . the highest antibonding orbital is
doubly degenerate; if the number is even, the highest antibonding ortital is nondegenerate:
Balya:nter -
The incre:!Sing number of nodes will result in molecular orbitals with symmetries (as
vioew.:d down the ring-metal-rit!G axis in the metallocenes) of u (complete cylindrica l

symmetry) ., (one nodal pllllle). 6 (two nodal planes). etc. These orbitals on the two
liGands can be added and subtracted to form ligand group orbitals (LGOsl. which in
tum can be combined with atomic ortitals of matching symmetry on the metal to form
MOs. For example. consider the lowest energy ligand bonding orbital. If the wave
functions for this orbital o n the two rings in the metalloc:ene are added. a Jlc>rodc> ligand
group orbital of the same symme try (a 1N) as an atomics orbital is produced. On the
other hand, if the two wave functions are subtracted. an llnRI.'md< ortituJ LGO or the
same symmetry as an atomic p orbital (u:,,) is obtained. In the ,S;Jme manner. other
LGOs .:an be constructed by either tldding or subtrtl.:t ing the higher molecular orbiJ>tls
of the two rings. The resulting combinations urc shown in Fis. rs.n .
Although symmetry considcr.ttions :tllow us to decide whm
:tre
possible, knowledge of relative eneryies und overlap intesruls is
in c1nlcr to
estimotte the nature of the resulting energy levels.Ill The ordering of the energy levers
has b.:en the subject of much discusslon.Yl Photoelectron sp.:ctroscopr stutlies in
conjunction with ligand field theory $Upport the encr11y levc:l diagrum for fcrroccne
... 1ni is ""' the plaa: 10 delve into the IUIIUJ'e or Of$:U'iC rill Sy>l<mS. FCK a discu.<SIOn uf the...:. sc:c
Lowry. T. H .: Ric:h:tnkon. K. S.
o..J Tit"""' in Ur,:nnlc- Chcmrsr,..; ll"'l'Ct and Row:
New Yorlt. 1987.
91 Tho$ n:fns to nodol pbne.< pcrpcndi:ulor 10 the pbnc ut the ""' Tllc rinJ: il>df _.., he " IIOibl
pbnc since Jbe syslcm is conSiruct< from :Mamie p orbl<ll.
"! Lauber. J . W. : Hcllinam. R. J. A"'. Clw111. s,.,.. t r16. WI.
YJ
Grohenik. P.; Grinttt", R.: Pcrutz. R. N.
.... .'i<IC'. R tm. 17. 43)-t!JO.
M.tallocenes
o(
od:tuls
F<
Cv
molIII-.U
AOs
LC.O.
671
orb1t,a.s
:==:==:t.:. .
4,..-
====: r..
00- .,.
SA.:)
..
..
8.J1_ -
- - - Ut
O
Fig. 15.32 LiGand l:fOOp orhit;>ls ami
atomic l)ft)itals on irun r,ll'
shown in Fig. 15.33.'"' The

orbitals of cyclopentulliene are so stable relative to
the mctul ()c'bitals th:uthey inter.tct but litlle. i.e.. the ligand is a poor udonor. On lhe
olhcr h:tnd . Ihe
orbitals arc so high in energy compared 10 the metal orbitals of
the s..mc symmetry thul they also inleract very little. which is anolher way of saying
lhatlhc sc empty orbitals arc not good :racceplors. The e 1,. anti a'!>, (4p) orbitals on the
iron atom arc at a high energy. anti so these orbitals likewise oo not contribute much to
the bonding. Tile only orbitals that arc well matched are "'" ring and metal (3d)
"'Grec:n. J . C. Stntf.'f. Bondin11 c&rlinJ t"l . 4J. }7-tt! .
672
l S O rgon-etalie Chemistry
u..nd
orbitals
Mcllllo<mo
orbital
...
cr,.,,'I"
p
c,.
..........,
d
Fig. 15.33 Qualitative molecular orbital

ror a metallocene. Occupation of IM
orbitals enclosed in the box depends on the identity of the metal; for ferroccne it is
(From Lauhet, J. W. ; Hoffmann. R. J. Am. Clttm.
1976. ll8. 1729-1742. Reproduced
w;th pcnnissioo. J
t.ui.
orbitals which form two strong., bonds. These Cp- M 1rbonds are believed to supply
most of the stabilization that holds the ferrocene molecule together.
If we supply e nough electrons to fill all the bonding and nonbonding molecular
orbitals but none of the antiboncling orbitals in ferrocene, nine pairs will be required.
Once again we see that the IS-electron rule is a rdlect.ion of tilling
stabilized
MOs. But how can we rationalize the existence of metalloccnes which do not conform
to the rule? Table 15.8 shows that manganocene, chromocene, and vanadocene are
one, two, and three electrons short, respectively, of 18. while cobaltocene and
Metallo.,....
673
Tahle 15.8
Propeoties of
bis(pentohaptocydo-
pentaclienyQ comple- of
lhe lint-row transition
m9tols
Compound
EJ.ctron
Unpaired
configuration
electrons
Cob
Purple 167-168
Cp2 V
'
Cp2Cr
..
Ci>zMn
Cp2 Fe
elRcTjR
Melting
point ('CJ
Scarlet
.s
Amber
172-173
172-173
Orange
173
Cp2Co
..
.l
Purple
173- 174
Cp2Ni
Green
173-174
nicketocene have one and two electrons in excess of 18. We also see that except for
ferrocene all are paramagnetic. The molecular orbital diagram of Fig. 15.33 allows us
to understand both the rule violations and the magnetic properties. The highest
occupied molecular orbitals
and a 111) are only slightly bonding and therefore
removing electrons from them does not greatly destabilize the complex. The e 1"
LUMO is not significantly antibonding so when electrons ue added to create 19electron and 20-electron species the stability loss is minimal. Although it is probable
that there is some change in the relative energies of the molecular orbitals in going
from complex to complex: self-consistent results can be obtained with the ferrocene
model.
As we saw in ligand field theory, so long as the d ifference in energy between a 1"
and e41 is less thnn the pairing energy, both levels can be occupied. Thus the three
unpaired electrons in
arc accounted for with its
configuration. To be
discussed later is C1>2Mn which has an
configuration consistent with its live
unpaired electrons. In this instance two of these electrons are found in the e 1"
antibonding level. Substituents on the Cp ring can be very influential in altering the
energy differences between MOs. With live methyl groups on the ring (pentamethylcyclopcntadienyl. Cp). spin pairing occurs and the electronic configuration becomes
af.,et,. suggesting that a crossing of the e!l! and a1" levels has occurred.
fe!K
r!Ka:.,r."
Structures of
Cyclopentadienyl
Compounds
r2Ra1"
The cyclopentadienyl metallocenes of the elements of the first transition series are
isomorphous and have melting points which are remarkedly constant at or near 173 "C
(Table 15.8). The structure of ferrocene in the solid state, originally described as
staggered, is now viewed as nearly eclipsed (a rotational angle of9" between rings)."
as are its heavier analogues ruthenocene and osmocene. The eclipsed configuration of
ferrocene is also favorable in the gas phase, where the rotational barrier is only 4 :!: I
kJ mor-. allowing the rings essentially free rotation. Neutron diffraction studies
reveal that. in the solid State. the hydrogen atoms of the ring are tilted toward the iron
atom.% The staggered arrangement is found for the Cp and decabenzyl derivatives
(Fig. 15.34) and r,esulls because of van der Waals interactions between the methyl or
benzyl groups of the two rings. The same interactions also cause the methyl and
phenyl groups to tilt away from the iron atom.
In typical metallocene compounds, Cp2M, all of the C-C bonds are of the same
length and the rings are parallel. However, there are several cyclopcntadienyl com9$
90
P.; Dunitz. J.D. Acto Crystollogr. St. B l979, JS, 1068-1074.

F.; Koetzle. T. F. Acta Crysto/logr.,
B 1919. JS. 1074-1081.
674

struc:Jure oC slliGBef'cd
dccabenzylferrocene. (From
Sc.h umnnn, H. ; Janiak. C.;
Kolln, R. D. ; Loc:beJ. J.;
Dietrich, A . J. Ortanum<t.
1989. J65. 137-ISO.
Rcptoduced with
permission.(
pounds in which the rings arc tilted with respect to one another.
are
Cp1 ReH. CP1TI01 and
(Fig. IS.3S). in which the steric requirements of
additional ligands prevent parallel rinas. Lone pair requirements in Sn(ll ) and Pb( ll)
result in similar tilting of the rinas in
and Cp1 Pb.97 Less clear are explanations
for bent structures in Cp;sr and Cp;& (Fig. IS.36). although packing forces may be
Finally, there are compounds with more than two cyclopentadienyl
Fig. 15.35 Some cydopentadienyl contplexes containing cilled rina.s
., Ccolnolly. J . W.: Holr. C. Ad.. Ortottt>m<'l. Chrm. t931. 19. 123-ISl. luld. P.: Hicl<dlcr. B.
Ort:-tullit:s
1201-1204.
"' Wilioon.., R. A.; Hanusa., T. P.:
J. C. J.
S.
19M.
OriiUN>tnnntlks 1990. 9. 1128-11)4. Blom. R.; FN;ri. K. Jr.: Vokkn. H. V. 0fllllt1tntH>Itlllirs
1990. 9. }72-379. MC)qes, G.; Hampel . F.: von
Schleyer. P. Or,r""""'""ifirs 1992. 11.
1769-tno.
""'5.
c.,.,,.,.,..
Metallocenes
675
Fig. 15.36 Solidstate structure of

Met:lllocene units are amngcd in
quasipolymeric chains and 3 ring-Ba-rin& tilt of 131 is <>b$c:rved. Lines conneclil\ll Ba and
meth)'llf'OIJPS indic:Jte the shorlest intermolecuLar COI\IXIS. (From Williams. R. A.; Hanusa,
T. P.; Hulfm:ln. J. C. J .
Soc. Clu:m. CoJmmmt. 1918. 1045- 1046. Reproduced with
permis_<ion.)
rincs. Examples in which severn!

are aUached to the same metal atom are
(tetmkiscyclopenl:ldienylltltanium (two rings an: .,.,' and two arc '1 1) and tetmkistetrahec.lrally. Fie. 15.35).
(cyclopenbc.lienyl)umnium (all rinss urc .,(and an:
A .Jilfercnttype of structure i the la)'crec.l
or nickel atoms and cyclopentadienyl rings in (CpJNi:(. as shown in Fig. IS.37... Complexes having I his arr:>ncemcnt are often called " triple: deckers" and hnve bt:c:n described with molecular orbital
lheory.99 A variety of cenlcr slices have been used in
of Cp. as s hown in Rc.
15.37""' Progress also continues in the syntheis
bonding theory of tetr.ukcker
s:uxlwich complexes.llll
There arc a few
knuwn huving only one cyclopentadienyl ring per
metal atom. Su.Jium C)'Ciupent;ulienide. cycklpc:nt;tdienylthalliumlll (vapor). and
tv.,ptwl have
thut muy be <lo:scrihcd as "open
J'accd sandY.ichcs." 111 : In the S<lli\1 . cyclopcnta\llcnylindiuml ll polymcrit.es to form an
infinite sandwich 'truc!ure
alternating cycfopcnt;ul icnyl
und indium alu ms.
In addition to
nlllnocydopcntadienyl compounds just tles,ribcd. ahcrc arc
many compounds which contain u sin{!le ring per mt!lal ;11om with a variety of
additional ligand$, such
carton monoxide. to complete the coordinulion sphere.
These include monomers and dimo:rs. with ;uxl withou t metal- metal bonds as necessary to obey the 18-o:lcctron rule . Some examples are shown in Flg. 15.38.
ur
"' loouhor. J. W.; EJi;Jn, M.; Summerville. R. H.; H<>O'nmnn. R. J. Am. Clom. S><:. 1!176. 911,
C....,.ky, P. T.:
M. IJ. J . Am. Ctno. St.,., 19114, 106. SIMI>-SIIQI. Jcmmi<. f_ D.;
Reddy. A. C.
t Wit, 7. 15tii-1$M.
,_ O:lvi.<. J . H.. Jr. ; SiM E.: On.nc.. R. N . J. " "' Clu:111. Soc-. 1"'9. Ill. 4n6-lnt4. Edwin. J.;
Gaa;<1'. W. E.; 8 U5h-ncr. C. H. (Jrj:u"''""''allk 19118. 7. 14116-1490.
'"'Jcmmi.<. E. D.: Keddy, A. C. J. Am. Clot,.,. Suo . IMO. 111. rn-r-1.
""'Ocxhlcy. 0 . T.. Jr. ; Bklm. N.: Cblrdlill . M. R.: Frqri. K.. Jr.; Fcttqcr, J. C.: P:Wk. J. C. ;
Vic:lori:tno. L. 0r,.'tlii<HrOt1ul''cl 1\1119, II. 146-)36.
676
150rganomelollic Ct..mislry
(b)
( 0)
( d)
(CI
Fig. 15.37 Some known ''triple dec.k ers.. containina cyclopenladienylligands.
There has been much discussion over the years regarding the C-C bond distances in the Cp ring. Five equidistant bonds is consistent with the electron delocalization found in the D"' cyclopentadienyl anion. If however, there are two intermediate,
one short, and two long C-C bonds, a structure closer to cyclopentadiene (C,) is
(9\ (9\ (9\

cJ\c
co
Oc
0
Rcd.()rqc Solid
mp 138'C
Air Sensitive
/ 1\
Ccc
(9\
(9\
Co
Ni
f<
Mn
c'J'
c ,
Yellow Solid
DOlt Brovm
mp7TC
AirSauilM:
mp (clcclll9'C
Solid
I\
Oorl< Red liquid

bp38'C
Aw ond He>l S.Nitivc
DOlt Red liquid

bp7LS 145"C
1'\upkRcd Soid
Rcd-Purpk Soid
mp21S'C
mp (dec) 194'C
Red Solid
mp (dc<:)IJ6'C
AirSalslllvc
AlrSloblc
Ail Sensitive
Fig. 15.38 Some commCI'cially available cyclopentadienyl complexes containina carbonyl

and nitrosyl ligands.
present and suggests localized bonding. It would seem that an X-ray analysis would
answer questions of this sort unequivocally but positional uncenainties caused by
thermal ring motion often present a problem. Low temperature measurements minimize these effects and in some instances it is clear that not only are there different
C-C bond lengths in the Cp ring but there are also smull deviations from planarity. In
Rh(Cp)(COJ,, C-C bond lengchs of 138.4(8). 144.5(8). 144.7(7), 141.2{8). and
141.()(7) pm have been measured and a small distortion from planarity has been
noted.o1 It follows that not all carbon atoms of the Cp are equidistant from Rh.
Distortions of Cp have mechanistic implications as well. When ReCpMe
{NO)(PMe:s) reacts with two moles of PMe3 T'Js.(;p rearranges to T'J1Cp:o.r
@;>
oN]
Re
' Me-
p, --.,..
ON-Rc-PM<,
Me
--.
(15.63)
As the five-electron donor oonverts to a one-electron donor. Re accepts an additional

four electrons from the two uimethylphosph.ine ligands. One additional mole of PMe3
causes loss of Cp- from the metal. It is highly likely that the T'J3.(;p complex is an
intermediate in the reaction although it was not detected. When Cp ligands are found
coordinated in arrangements other than the symmetric -,t. we sometimes refer 10 them
as ..slipped" ring systems. The rhenium reaction is an extreme e xample in which the
ring has been induced to slip completely off the metal atom (Tis T'J1 TJ 1 TJ0 ). Thus
one. two. and three vacant
sites become successively available on the
metal in this reaction. Jndenyl
have attracted much auention because they
undergo s ubstitution reactions much faster than Cp complexes. tO$ It is believed that
an 7]1 intermediate is stabilized by formation of the aromatic benzo ring. tOto
===
101
Lidltcnbcrger, D. L.; Blevins. C. H. II ;

R. B. Ori(U'Idllltlnlilt:s 1984. J . 1614-1622.
Fitzpauick. P. J.; LePage, Y.; Sedman, J.: BI.Cicr, I. S. lnur11. ctm. 1911 , 10,
O' CCJMOr. J . M.; Casey, C. P. Clttm.

19117,87, ](11.
""A rina slippaae mechanism was first propc>IC<! in 1966. For a discussion <:IIIIis work. see Basolo. F.
100
Polylrtdrun 1990. 9, 1503-UJS.

""'Habib. A.; Tarilct, R. S.; Holl, E. M.; crobtn:e. R. H. OrttutDmtta/Jics, 1919. &. 122S-1231 .
678
15 Org.,.,oMelallic Chemistry
We have already seen that metallocene complexes often violate the IS-electron
rule and that stability of these violators can be attrillllted to the nature of the molecular
orbitals to which electrons are added or from which they are removed. In view of this
eleclr'onic flexibility. it is perhaps not surprising that Cp ligands are capable of
stabilizing a wide range of oxidation s tates. Normally we think of organometallic
chemistry as being the domain of low oxidation state complexes, too but increasing
interest in high oxidation state complexes is apparent and often the cyclopentadienyl
groop is p resent as a stabilizing ligand. to& Oxidation of cyclopentadienyl complexes
may lead to isolable oxo complexes as shown by the following hydrogep peroxide
reaction.
(15.65)
Some other oxo complexes are shown in Fig. 15.39. Although the oxide ligand is
generally thought of as c;- rather than neutral 0, its similarity to the carbene ligand.
CR: (which could also be viewed as
tends to be obscured as a result. Interest
in oxo complexes is tied to their relationship to metal oxide catalysts which are widely
used in OfGanic synthesis.
Covalent versus
Ionic Bonding
and CPlCo are considered to have strong

Mctallocenes such as CPlCr,
covnlent bonding between the metal and the rings. Although not all of these metal
lo&:ei'ICli are stable with respect to oxidation, etc., all have strong bonding with respect
to dissociation of the rings from the metal atom (fable 1.5.9). The bonds between I he
metal and rings certainly have some polarity. but these compound.s d o not react like
polar organometallic compounds (as exemplified by the weU-known Grignard reagent):
+ H2 0
Cp,Fe + H 2 0
RMgX
+ MgXOH
---+
RH
---+
N o reaction
(15. 66)
(15.67)
fig. 15.39
tadienyl complexes in
wtlich the metal in a
higll oxidation state.
"" F.ven CO. which """"""Y hU

1111\nily for melnls in high oillotion
hal< hccn fOUild in
Su. F.M.: Cooper. C.: Ocib. S. J.: Rhei,..okl. A. L. : Muycr, 1. M. J.
Am. CA<"m. S. lf86, /08, lS4S-JS47. Allt)'l J1t0UP5 may alto Slllililtu high oidation tGtcs, c.c..
WM.,.,.
""' Bouomlcy. F.; Sulin. N. AJv. Orl/d110'11<1. Clwm. 19111, 18, )}'1. LcJ1<li"", P.:
E. C.:
S.tnchCJ;. L.
19119. 11. 940-'#49. M......man. R. W.: Sllost.,, J. M.: Willi<ln, S. R.:
Sh:lplcy. P. A. Orl/onotrtttuilia 1,1. /0, 1671- 1676.
Metolloceftes
679
In contr:tSt. several compounds are known which contain a very reactive C5H, group:
NaCp + H 1 0 -
C,H 6 + NaOH
MgCP2 + 2H 20 SmCp3
+ 3H1 0
(15.68)
2C,H6
+ Mg(OHh
(15.69)
3C,H6
+ Sm(OH)3
(15.70)
These compounds are considered to have a suit-like nature and are usually referred to
as metal cyclopentadienides rather than as cyclopentadienyl
although the
distinction is sometimes rather arbitrary. As is the case with all polar bonds. there is
no sharp distinction between
and ionic bonding. Thus. although the lanthanide compounds are usually referred to as ionic. there may be a substantial amount
of covalent character present.
The beryllium and magnesium compounds are of special interest with regard to
the problem of covalent versus ionic bon<.ling. Although magnesium cyclopentadienide
(magnesocene) is structurally almost identical to ferrocene. it is thought to be essentially ionic. The sandwich structure should be the most stable one not only for
covalent complexes Ulilizing J orbitals. but also from an elect.rostatic viewpoint for a
cation and two negatively charged rings. The structure of the beryllium compound is
unusual and still somewhat uncertain. 1<l'J Its large dipole moment rules out a ferrocenelike structure. and a single 1H NMR
even at low temperatures. indicates a
fluxional mokcule. Both X-r.ty and electron diffraction data have been interpreted in
terms of a "slipped sandwich"' complex !Fig. 15.401 in which one Cp ring is penlalmpto and the uther is either weakly TT bonded or
even <r bonded. Most
recently. solution mkrowave dielectric loss measurements have been interpreted in
favor or two equivalent rocking structures with an oscillating Be atom (fig. 15.401>).11
lk
1.\J ,.,..,
.---
tk
lk
11\l t"
__.;
__;,_
'"'
Fig. 15.40 POSJulalro structures of tC,H,>,Be. (a) Slipped sandwich in which one rinc is
pcn13h3f!IO and lhc other is monohaplo. (b) In solution the Cp rings appear to rock as the
beryllium alom oscillalcs. [From Prnucn. S. J.: Cooper. M. K.; Aroney. M. J.; Filipczuk.
S. W. J. Ch,m. So><'. Dalton Tr<lns. 1985. 1761-171>5. Used wilh pcnnission.l
'"" Julzi, P. tid.

Ch,m. t 9H6.
ti<"ID 19'11. iYfl-l1JIJ. 309-JIK.
217-2?5. Rcollic. J . K.: Nut;cnt. K. W. l>rt'lrl/. Chim.
'"' Pmttcn. S. J .; C>op:r. M. K.: .... runcy. M. J.: Filipczuk. S. W. J.

1761- t76S.
So>e Dvllun Trans.
t985.
480
15 Organometallic Chmislry
One form of manganocene. C1>1M n , consists of infinite chains of CpM n fragments

bridged by cyclopenladienyl rings in the solid. II I Upon being warmed to 159 c the
color changes from brown to o range and the product is iso morphous with ferrocene. It
hus been formula ted as ionic, high spin d 3 , Mn2+2Cp- . Evidence for ionic bonding is
or three types: (I) Manganocene reacts instantaneously with ironll chloride in tetra
hydrofur:m to form ferrocene and is hydrolyzed immediately by water: (2) the dissociation energy (Table 15.9) is closer to that of magnesium cyclopentadienide than to
those of the other tmnsitio n melal metallocenes: and (3) the magnetic moment of
manganocene is 5.86 BM, corresponding to five unpaired electrons. All these data arc
consistent with a d' Mn2 + ion. The evidence is not unequivocal. however. Other
melallocenes such as chromocene react with iron(IJ) chloride to yield ferrocene as
well , although admittedly not so rapidly. Assignment of "ionic bonding" to manganocene on the basis of its being high spin Mn(ll) is reminiscent of similar assignments to other high spin complexes. The presence of high spin manganese and a lower
dissociation energy for manganocene indicate the absence of strong covalent bonding
(i.e . , a small ligand field stabilization energy from the
configuration) but do
not preve nt the possibility of some covalent bonding. In any event,the stability of the
half-filled subshell, d 5 configuration is responsible for the anomaly of manganocene.
This anomalous behavior d isappears whe n methyl groups replace the hydrogen atoms
of the ring (page 673). The Cp;' Mn complex is low spin (one unpaired electron) and
has chemistry similar to that of other melallocenes.
Synthesis of
Cyclopentadienyl
Compounds
Tai>M15.9
Dissociation ..-gies, D, of
metolJoceneso
The first metallocene was discovered by accident independently by two groups. In one
group. an auempt was made to synthe.size fulvalene by oxidation of the cyclopenladienyl Grignard reagent :112
0 0
o-
Fe' ' - .,_

Mg-X
Metal-
DfM- Cp} (kJ moi-
clllv
369
Cp2 Mn
Cp2 Fe
Q12 Co
Cp2Ni
279
212
302
283
258
cP2Cr
-""
US-71)
J"
Chippcrfoeld. J _ R.: Sne)'d, J. C. R.;

Webster, D- E. J _ Organon"'- Cht m .
1m. 178, tn-t89-
are avenge dissociation

maies based on 1)(11:-baJf of the
energy required f Jhe re3Ction,
Q>:M(a)--. M(a) ;!' 2CNI-
'" BlOnder, W-: Weiss, E. Z. Nat11r/orsch. B: A110rg. Chnn .. Org. Chem. 1978. JJ. 123S-1237.
112 Kealy, T- J. ; Pauson. P. L Nature J9St. 168. 1039-1040.
Metollocn
681
The synthesis of fulvalene was unsuccessful."l but a stable orange compound was
isolated which was subsequently characterized and named ferrocene. The iron( Ill) is
first reduc:eO by the Grignard reagent to iron(II) which then reacts to form ferrocene:
(15.72)
Sodium and thallium cyclopentadienide provide more versatile syntheses offerrocene

and other metallocenes.
MX2 + 2NaC,H,- Mlr/-C5 H5>z + 2NaX

Thallium cyclopentadienide is often used when the reducing power of the sodium salt
is too great. The l.imited solubility of the thallium complex in organic solvents and its
toxicity are its chief disadvantages.
Ferrocene. the most stable of the melallocenes. may be synthesized by methods
not available for most of the others. Iron will react directly with cyclopentadiene114 at
high temperatures (ferrocene was discovered independently by this method liS). Use
of amines facilitates the removal of the acidic hydrogen of cyclopentadiene. allowing
the synthesis to be accomplished at lower temperatures:
(15.74)
Fe+ 2(R,N H)CI - + FeCJ2 + 2R,N + H 1

FeCI2
+ 2C,H6 + 2R,N
Net reaction: Fe+ 2C,H 6
Alene Complexes
Fe{'1'-C,H,h
+ 2{R 3NH)Cl
Fe{I)'-C,H,h + H2
(15.75)
(15.76)
Ahhough the cyclopentadienyl group is the best-known aromatic ligand. there are
several others of considerable importance. None leads to complexes as stable as the
most stable metaUocenes. however. and the chemistry of t he complexes that do form
is more severely limited.
Benzene and substituted benzenes normally act as six-electron donors. although
dihapto and tetrahapto complexes are also known . Dibenzenechromium was prepared
early in this century but was not characterized untii i9S4. It was first synthesized via a
Grignard synthesis. When PhMgBr reacts with CrCI3 in diethylether solvent. a monohapto complex
forms which rearranges,ll6 presumably by a free radical reaction to give. among other products. (Cr(1]6 -ChH6hl +. This ion can be reduced
to the neutral metaUocene.
PhMgBr
('ret,
[CrPh 3(Et:Ol3)
Na.S.O..
---=...:......
(15.77)
Arene complexes are synthesized more cleanly by the fischer-Hafner adaptation of

the Friedei-Crafts reaction. In this reaction aluminum is used to reduce the metal salt
oniy as a trllllsicnt spccM:s: how<:ver. it is Slabilized when

coordinntcd 10 o variety of trnnsition mo:tal atom. . For a leading reference, sec Moulton. R. D.;
Bard. A. J. Otgonum.,olllcs 19811, 7. 351- 357.
m Fulvalcne is hit!hly unstable and exists
u Typically instCild of sJarti111: with cyclopentndicne. 0<1C begins with its !Mis-Aidcr product.
dicydopmtadicne. This compOUnd crncks when heated 10 give cydopenlndicnc.
"'Milia". S. A.; Tebboth. J. A.; Tremain. J. f . J . Cht m. S<.c. 1951. 6JZ-(,J5.
116
Ple<!s.: note that v.t>eteas monohap(o and penlahapto Cp are isoma"s. phenyl a nd benz.cne lipnds
differ by a hydrogen atocn.
682
15 Organometallic O.emiatry
ro a lower oxidalion stare and wirh lhe assis.ance of AICI 3, benzene is coordinaled to
chromium:
(15.78)
The calion can be reduced to dibenzenechromium with sodium dirhionire.
The dibenzene complexes of Cr. Mo. and W are all air sensitive and rhose of Mo and
Ware especially so. Dibenzenechromium is a black solid rhat melts at 280 c.
The success of the Fischer- Hafner method depends upon rhe particular arene and
on lhe skill of the experimenrnli.st. Several decades ago Timms introduced a chemically innovutive approoch for making a variety of organometallic complexes.t t7 It is
based on the premise that if you wish to synrhesize a zerovalent complex. ir is logical
to begin with metal atoms rather than wilh salts thai must be reduced. Highly uctive
meral <Horns can be created by vaporizing metals under vacuum with resistive heating
designed
and rhen condensing rhe atoms on low-temperarure walls of a
vessel (Fig. 15.41). 118 A ligand. benzene for example. can be inrnxluced into the
vessel where it will react wirh the metal atoms to form a complex.
M(s)
--+
M(g)
M(rl-C,HJ2
(15.79)
f'og. 15.41 An inexpensive apparatus constructed from a modif>ed rotati11g evaporator and
uSI.-d to vaporize metals for coodensation with ligands. [Adopted from Martie. R. J .;
Peuijohn. T. M.; l:lgowski. J. J.
1985, 4. 1.529-ISJI. Used with petmission.J
Mo<lifocd
CVliPOfUCut
WOJAY-<eokd
k'..W.
117
HiGh
Tunm. P. L.; Turney. T. W. Adv. OrgatttJmrt. Clutm. 19n. U. SJ.

" "Klabunde, K. J. Ace. Chrm.
11115.8. 39J..J99. Markle. R. J. ; Pcuijuhn. T. M.; l.ugoWl<ki. J. J.
OrgttllntnrtofliN 1985, 4. 1529-ISJI.
Metallocenes
683
The rings of the dibenzene chromium. molybdenum. and tungsten complexes are
eclipsed and have a small rotational barrier. Unlike ferrocene. these complexes have
labile rings which can be displaced:
(15.80)
The benzene rings can be removed completely by reaction with a more active ligand:
(15.81)
There are a number of heteroatom six-membered aromatic rings which are :malogous to benzene in that they can donate six electrons to a metal. These include
phosphabenzene. borabenzene anion. bornzine. and arsabenzene shown in fig.
15.42. 119
Cycloheptotriene
and Tropylium
Complexes
Cycloheptatriene is a s ix-electron donor that can form complexes similar to those of

benzene but differing in t he localiz:.tion of the 1T electrons in C7 H. The alternation in
bond length in the free cyclohcptatriene is rctai noo in the complexes (fig. !S.43).
Furthermore. in C,H.MoiCOl, the double bonds
located trans to the cartonyl
groups. providing an csscnti;llly octah .."\\r.ll e11vironment ror the metal atom .
f'og. 15.42 Complc:.es of phosph:.b<nzcnc.

bornzinc. and arsabenzcnc.
mx--mbered
are analoJ:OUS so b<nzcno:. i.e .. they are six-elecrron donors and are
aromatic.
"" Etschenhroic:h. C.: Nowulny. M.: Melz. B.: Mn.'-"' W. ; Grnutich, J.: Bichler. K.: Snuer, W.
An,rew. Chtm. Int. &/. nNI. I'J'Jt. JU. s-17-SSO.
684
II
II

structure of tric:nrbonylcycloheptauienernolybdenum(O) iDustralina
alternation in bond lec1glhs
and location of double
bonds trans to the crubonyl
ipnds. Bond lengths are in
picomctel"$.
Cycloheptatriene complexes can be oxidized (hydride ion abstraction)" to form

cycloheptatrienyl (some.times called tropylium) complexes:Jzo
(15.82)
Mo
/I\
+ fh;.CH
c cc
O
0 0
c-c
The tropylium ring is planar with equal

distances. Like benzene and the
cyclopentadienide anion, the tropylium cation is an aromatic, six-electron species.
Cyclaoctotetraene
and Cyclobutadiene
Complexes
In accord with the Hilckel rule of 4n + 2 electrons, both cyclobutadiene and cyclooctatetraene (cot) are nonaromatic. Cyclooc.tatelr.lene contains alternating bond lengths
and has a tub-shaped conformntion:
This nonplanar molecule becomes planar on reaction with an active metal to produce
the cyclooctatetraenide anion (cotr- .t2
(15.83)
20 TropYiium
salts. such as tC7H7)8r. are not used direc:lly for organotnc:Jallic synthesis because of
thcir oxi<hing power.

121
Dry K,C.H.c explodes violently upon contact with air. Gilbert, T . M.; Ryan, R. R.; Settelbe(Jer,
A. P. OrganomrlaUics 19&&. 7. 2514-2518.
The cot dianion. like Cp-. is aromatic but has ten electrons in eight.,. orbitals. When it
is allowed to react with tetrnpositive actinides. such as u, Np4 , Th4 +, Pa... and
PuH. a neutral metallocene resuhs.tn
UCI. + 2cot 2 - ---+ U(cot)z
Fig. 15.44 Structure of

uranocenc sllowing the two
eclipsed c:ydooc:tntetracnyl
rings.
(J5.84)
The uranium compound was the first metallocene of cot2 - to be synthesized. Ill A
sandwich structure was proposed for it and later verified (Fig. 1.5.44). 124 By analogy to
ferrocene it was called urnnocene. The extent of covalency and the Sforbital contribution to the bonding in lhese complexes has long been debated . Recent photoelectron
spectroscopy results12.S and ab initio quantum mechunical calculoJionsll6 support
significant covalency and f orbital involvement. A molecular orbital scheme suitable
for urnnocene is shown in Fig. 15.4.5. Missing from the diagram are the low-lying
nondegenernte a 1 and
orbitals. which house four of the 22 valence electrons.
These are primarily ligand orbitals and do not contribute significantly to metal-ligand
bondif1&. The remaining 18 electrons fill the r 1
l'!JI and r:!u levels and leave the
r3o, level half filled (two unpaim:l electrons). The r 21, LGO donates electron density to
the
(Sfxr.
orbitals and the r !N LGO donates electron density to the .r.:r..
(6d_.:- ,;. 6dxyl orbitals of the uranium atom . Neptunocene (S/1 ) and plutono<:ene (SJ )
have one and no unpaired electrons, respectively, as predicted from Fig. IS.4S.
The lanthanides might be expected to rorm similar complexes, using 4f orl>itals in
place or the .5/ orbitals of the actinides. They do so. generally forming
complexes (Dad), although Ln(c:ot)O species are also known.m These complexes are
viewed as essentially ionic with minimal 4f covalent participation.
Cyclobutadiene, C4 H4 , eluded synthesis for many years because or its reactivity.
Although simple Hiickd theory predicts a square molecule with two unpaired electrons. infrared studies carried out at low temperatures (it dimerizes at 3.5 K) have
shown that it is rectan(!).llar with alternating single and double bonds. In addition. all of
its electrons are paired. More sophisticated MO treatments are in acconl with these
results. In 1965. a great deal of excitement was generated when a complex containing
coordinated C4 H4 was
(JS.85)
Thus cyclobutadiene, which was nonexistent at the time. was shown to be stabilized
by complexation. Oxidation of the complex liberated free cyclobutadiene which was
trapped by ethyl propynoate to give a cycloadduct. The experiments established that
'"' Mmb: T . J. Prot:. lnorg. CMm. t919, 1J, 224- ll).
IU Stn:ilwieKr. A .. Jr.; Milller-Wc:stcrl>oft', U. J. Am. Clttm.
1961. 90. 1364.
' " Zulkin. A.; Raymond. K. N. J. Am.
Soc. 1.969, 91, 5667-S668.
ru Brennan. J . G .; G reen J. C .; Redfern C . M. J . Am. Clttm. Soc. t989, Ill. 2373-2377.
'"" Cllang. A. H. H.; Pit=, R. M. J. Am. Cltnrr. Soc. 1989, 111. 2.l00-2.S07. llunlm, 8 . E.; Bums.
C . J.
l""'f. Clttm. t989. 9. 61- 100.
T. J. PtDg. lnorg. Clttm. t978, U . St-t07.

ru Emerson, G. F.; Walts. L ; Pdlit, R. J. Am. Clttm. Sot-. 1M$. 81, IJI-Ill.
121 Marlc$.
686
1 5 Orgonomtallic Chonitry
f"tg. 15.45
(I)
(a)
Moleculnr
orbillll dlll&mm for

I
'Jo
actinoc:ene, Ani'I".C.H.J;:.
,','=t,,
tx/--4.":.. - - - G
a actinide metal).
(b) Interaction I orbital
the metal with a tipnd
t'1u orbital. (C) lnlerac:tion
cl d orbital of the metal
orbital.
with a liga.n d
(From Brennan, J. G.;
Green. J. C .; Redfet"n,
C. M. J. Am. CMm. Soc.
1989, /II, 2l7l-23n. Used
(An
or
or
c._.
with permission.)
...
' -="':,.,=
', =--
'
'
cyclobutadiene could exist. however briefly. and led eventually toils low lemper:uure
Reactions of
Organometallic
Complexes
Substitution
Reactions in
Carbonyl
Complexesl 29
The e<lrliest methods of replacing one or more carbonyl Ugands from a

relied
on brute force (heat or light) to break the M-CO bond.tJO The idea was chat once the
CO had dissociated, it would escape easily from solution ai'KI chus have
minimal chances of recombining with the metal. The depanure or CO from a complex
leaves a vacant coordination site and in genernl an unstable metal fragment which is
electron deficient. The fragment can lhen react with a nucleophile such as a phosphine. RJP. to produce a substituted metal carbonyl . The entire dissociative process
can be described as follows: Ill
o:.o Alhc:n. M. G.; Ccwile, N. J. C<HNJ. Clt<-lft. RI'V. t914. JJ. :!27-139.
uo 'The use of ullra$001111 as an o:nc:fll.Ysoura: rur btcultitll the M-ro ooml al>o 11M bn invc.tipJed. SusiM:Ic. K. S . Adv. 0rrDIIO<rWI. C*m. 1916. 1:S, 73-119.
u o 11..-. I , he nics o( sub.uiwlion reaclions for
ccmplexeo are neurly irodq>mdent o( the
<> IJi ir.coming ligand .micb supporll a diuoc:iatioe mcc.honi'ltll.
-----
Reactions of Orgonometonic Comp.. x..
687
L,M-CO ....,.. L,M +CO
(J5.86l
L,M + R1 P
(15.87)
---+
L.,.M-PR3
Of course some complexes lose CO more readily than others. For example. it is rather
easy to displace all four CO groups of Ni(C0)4 with L <L = R3 P) in stepwise fashion:
2.....
Ni(COhL
2.....
N"l(CO)zL2
2.....
Ni(CO)L,
.-!:......
NiL4 (15.88)
The task is much more difficult for

which has a large energy of activation for
substitution and requires high temperatures. At these temperatures side reactions are
significant and yields of substituted products are low:
Fe(CO),
.-!:......
Fe(C0)4 L
.-!:......
Fe(COhL1
(15.89)
Notice that Eq. IS.89 shows only two CO ligands being displaced . Elich time CO is
replaced by R3P. the complex becomes more electron rich and the remaining CO
groups receive more., electron deru;ity. This means that in general the M-CO bond
strength increases and CO becomes more resistant to dissociation. Of course the steric
requirements of the phosphine may limit the degree of substitution as well (see cone
angles. page 688).
The thermal and photolytic reactions described
usually give a mixture of
products and therefore are not us popular :Is they once were. Reactions have now been
developed which give a good yield of the
of interest. For example. if
one wishes to prepare
one would not heat W(COJ. with PR3 at high
temperatures or Irradiate the reaction mixture with ultraviolet light because both
of these methods would give mixtures of
d.T-W(C014 !PRJI:!
and perhaps facial or meridionaltrisubstitut.:d products as well.
A preferable approach would be to first prepare
by photolysis of WIC0)6
in thf and then. without isolation of this complex. disphu:e the thf with the phosphine
in a subsequent room-temperature reuction:
W(CO) + thf
W(COhthf + CO
+ PR1
---+
(15.90)
+ thf
(15.91)
T
is a sullicicntly puor ligand that it o;cldom displaces more than one
CO group in the photolysis step ;md thus the reaction yields tl1c m<mosubstitutcd
product exclusively.
Another twist is to add Me1 NO which allacks the carbon or., coort.linatec.l CO.
kudingto eventual loss of
and formation of un unstable
complex.
The phosphine easily displaces the amine to form the tinul product:
(OCJ,WCO +
(C0)3WNMe3 + C02
tOCJ,WPR 1 + Me1N
(15.92)
The preparation of pure Fe(C0)4 PR3 and /rcms-Fe1C0)3{PR 3J2 have long been
fmslrating because
and photolylic methods give mixtures of products which
arc not e..sy to separate. The
complex may now be
by
several routes. one of which involves cobalt( II) chloride as n catalyst:
Fe(CO)s + PR 3
ColO,
----+
Fe(C0)4 PR 3 + CO
(15.93)
The exact role of the catalyst in this re..ction is unknown.m Alternatively. the
reaction may be catalyzed by polynuclear iron :lnions. such as
or
m Alhc<s. M. 0.:
385-390.
J. H.: AshwMh. T. V.; Singleton. E. J.
Clt#m. t981. 217,
688
lSOrgonometallic O.emistry
[FeJ(C0) 11 J2 - .m A successful method for producinG the trans disubstituted complex

is to create [HFe(C0)4 r and allow it to react with PR, in refluxing
Fe(COls
[HFetC0)4J- + 2PR3 + BuOH -
[HFe(CO)J- +CO
(15.94)
trans-Fe(C0h(PR3)a + CO + H! + Bu0(JS.9S)
The countetion is quite important to the o utcome of this reaction. !on pairs. which
form between alkali metill ions and the complex. induce CO lability which aids in the
substitution process. " Large charge-delocalized cations such as PPN+ are much less
effective in forming ion pairs. The substitution process shown in Eq. IS .95 occurs
readily wben the counterion is Na+ but fails wben it is PPN+. Another good example
or this effect can be seen by comparing Na(Co(CO)J and PPN(Co(COJJ. 1ll> The
former is readily substituted by ' JCO. phosphines, and phosphites. while tbe latter is
iner1 with respect ro substitution.
Ugand Cane Angles
It is intuitively obvious that the space occupied by a ligand can influence not only how
many will fit around a metal atom but ill$0 t.h e effectiveness of overlap between metal
:md ligand orbitals. If ligands are too crowded, repulsion between them forces
metal-ligand distances to increase, weakening tbe metal- ligand bond. and enhancing
the overall lability of the complex. Though steric effects have been long discussed in
the literature. only afler Tolman introduced the concept of the cone angle in 1970 did
inorganic chemists have a quantitative means of expressing these ideas.tl7 Jt should be
clear that for a ligand such as PhJP. the C- P-C bond angle does not give a
satisfactory measure of its space requirements. It is the volume of space taken up by
the three phenyl groups on phosphorus that is crucial and a simple bond angle does not
rellect this information . From a study of zerovalent nickel complexes, NiL4 (L =
rhosphine or phosphite), Tolman observed that the binding ability of a ligand depended stronGlY on its stetic needs . He concluded that he needed a way of measuring
I he cone created by the phosphorus ligand. Not all good ideas require an expensive
pie.:c of .:quipmem. With a block of wood, a nail, a space-tilling model of e;ach ligand.
and an all<lChment for measuring angles, he wus uble to. do what was required. The
measuring device is shown in Fig. IS.46a and the cone angle, de lined as the apex angle
of a right cyclindrical cone, is outl ined in Fig. IS.46b. The distance from the center of
the phosphorus atom to the tip of the cone, 228 pm. was chosen on the basis of the
nickel-phosphorus bond distance. Cone anale values for a rwmber of ligands are
shown in Table 15. 10.
Ligands such as CO are stetically undemanding and as many as required by the
IS-electron rule can easily arrange lhemselves around a metal atom. When bulky
" ' Bulls. S. B.: Shriver. 0 . F. J.
Ortm. t979. lf>P, 191- 197.
' " Koitcr. R. L.: Kciler. E. A.: HeckC7. K . H .: Bocd<cr. C. A. Or,:oN>mtUJifits t9111. 7. ZAM-2.u.!l.
AMI. C. E.: Odord. T.: Simmons. 0 .; Darensbolq. M. Y. 0r,:oi'I<Hnttul ic-. t986. J, 17-25.
,,. Ungv:iry. F.: Wojcic:lcj, A. J. Am. Clo#m. Soc. tm. 109. 68411-6849.
ll'7
Tolman. C. A. Chtm. Rtv. tm . n.lll-348. For some ncwdcvclop'ncnts in lhiswu. see Brown,
T. L ,,.,.,, Clttm. 1992, J/,
.
Reaction a l OrganametaUic Ca..,p!e..s
689
Fog. 15.46 Device ror

determining cone angles.
(From Tolman. C. A .
Cl.,m. Rr v. t977. 77.
l 13-348. Usa! with
pcrmi$$ion.l
,.,
phosphines are part of the coordination sphere. however. it becomes incre:asingly
difficult to satisfy the 18-cfectron rule ,gmply because there is not enough space for the
number of ligands. It is not difficult to replace three CO groups of Mo4C0)6
with three phosphines having modest cone nn&les. When Ppr,. which has a cone angle
of 160". is chosen. however. it is only possible to replace three CO croups with two
phosphines. The result is that a Jl>-elcctron species is sterically stabilized. We saw
to cive an 18-clectron
earlier (Eq. 15.31). that H: may be atkled 10
complex, and this iUustrates an important point. namely that complexes containing
bulky ligands may have vacant coordination sites. bul they are available 10 only the
smallest donors . Often this idea can be used to advantage in designing syntheses for
organometallic complexes.
A further example of l:lrge ligands blocking out smaller ones to give low coordina
tion numbers is provided by the wor1< of 0tsuka. 1311 Phosphines with small cone angles
such as PEt, ( 132") allow isolation of Pt<PEt ,)4 which obeys the 18-ekctron rule. bu t
ligands with. cone angles greater than 160" m'a ke it possible to isolate complexes with
just two ligands. e .g..
It is also observet.l thot bulk)' ligands avoid beinc .:is to one another..oo In a series
of octahedml
tL
phosphine I complexes. the pc:rcentase of trans isomer
isoh1ted from a
reattion incren.scs as the cone angle of the phosphine
increuses (Table I.S. II ). Electronic factors favor cis arrangements. but stcric factors
become dominant as the cone angle increases. Attempts to synthesize Fe(CO))(PBu)J:t
have failed because the large cone angle of the phosphine ligund prevents coordination
of more than one of them.
Oxidative Addition
and Red uctive
Eliminatio n
One of the most imponant classes of reactions in orcanometallic chem;st;y ;., :errr.e7
oxidative uddilion. In these reactions a coordinatively unsuwrated
in a
relativc.l y low oxidation state undergoes 11 formal oxidation by two units (loss of two
'"'Otsuka. S. J. Or_.._. Orrm. 1910. !(}(), 191.
'"'The r<Cenl <Yillllcois ofll'h,P):N !Ural:l. H.:

lm . .l64. 2J5-:441shows !holt
H.:
Y.: lkaw.1 T. J. OrJI""m""
number of: m;ay be inducal with """"wh>l
smoller cone :uwJes ll'hJP: 14S.,

... Sh-. B. L. J . Orgtntomn. Clrrm. t910. 100. 307-318.
Table 15.10
Con Clflgles, B, 101' ""rious
ligo..ds, l
101
1'(0CH2 )3<:a
PPhH,
P(0Mel3
P<0Et)3
P(OCH2CH1Cl},
PMe(OEI)z
106
107
109
110
112
117
PMe,
P(0Me12 Ph
P(OEt)!Ph
PM e. Ph
PPh;H
PIOPh),
1'(0-i-Pr),
P{0Me)Ph1
PEl,
PBu,
P(CHzCH2 CNl,
P(0Eill'!7
PMe(iBu)z
PEI. Ph
PEIPh,
P(Q.o.toll)
PPh:(CH2CH1CN)
P(OC)'),
P(i-Bu),
PCy2 H
PJ>h,
118
120
121
122
126
128
130
132
132
132
132
133
135
136
136
136
140
141
141
141
143
143
14S
145
14S
14S
145
145
P(p-CF)<:.HJJ
14S
152
P(I-Prh
PCy1 Ph
PBzJ,
P(m-toi)J
PCy,
P(t-Bu)zPh
P(t-Bul,
NHl
NH2 Me
NH2 Et
NH2Ph
NfiA'
NHMez
Piperidine
NHEt.
NHcY1
NHPh1
NE13
NPh,
NB:tl3
H
Me
F
160
162
165
165
170
170
182
94
106
106
iSJ
Il l
115
119
121
125
133
136
ISO
166
210
7S
90
92
95
102
102
co
El
8t
lOS
Ph
I
lOS
107
1-Pr
114
P{p-CIC6 HJ,
1-Bu
126
Plp-FC,.HJ,
ptp-Me:NC.HJ,
R.ahman. M. M.; Uu. K-Y; Erika. K.: Prude. A.;
Gic:m,, W. P. Orgonomtlnlli<s 1989,8. 1- 7. Tolman.
C. A. CMtn. Rtv. 1977. n. )13-)48. Sclipon. A. L
Truglcr, W. C. J . Am. Chtm. S. 1991. IIJ,2S!o-!S27.
Table 15.11
c- Of19les Olld rcmos ol

C.ttmms-.n ioo
W(COJ4 L2 complex..
!he reooion:
WJCOJ.(tmpo)
+ 2l
PPhzH
--+
W(C0)4l 2
%C.
........
P(p-101),
P(o-tol)3
126
140
JS7
14S
194
100
38
21
21
0
--
%trans
0
62
79
79
100
Lukehart. C. M. FunJo-lllof Ttlfrultion

Orgunomttall/c Chtmi$/ry; Brooks/Cole: Monterey, CA.
198S. for 1111 but
b from the authors'
690
Reactions of 0'11onometallic ComplexH
691
electrons) nnd at the same time

its coordination number by two. An example
is the reaction of Vaska's complex with molecular hydrogen (Eq. 15.28). In this
instance. iridium is oxidized from + I to + 3 and at the same time the coordination
number of the complex increases from 4 to 6. The reverse reaction, in which H, is lost
in
from the complex. involves reduction or iridium from + 3 to +I and a
coordination number from 6 to 4. This process is called reductiv" elimination. This
specific example of oxidative addition/reductive elimination may be generalized as
follows:
(15.96)
In order for oxidative addition to occur, vacant coordination sites must be available. A
six-coordinate complex is not a good candidnte unless it loses ligands during the
course of the reaction making avoilable a site for interaction. A further requirement is
that suitable orbitals be availnble for bond formation. An IS-electron complex such as
[Fe!COJ..f- has only four ligands but adUition of X - Y would require the use of
antibooding orbitals, which of course is not energetically tll.vorable.
Mechanisms for oxidative additions vary according to the nature of X-Y. If
X-Y is nonpolar, as in the case of
a concerted reaction leading to a threecenteRd t.ransition state is most likely.
L
co
oc I
.H
' Jr..+H.'- Jr:: I
0/ 'L
Cl/1 ' H
L
oc I
'- Jr /
Ct/1 'H
L
(15.97)
Nonclassical complexes of dihydrogen

b4S) may be thought of as complexes in
an arrested tr.tnsition stnte and their exis tence provides strong support for a concerted
reaction mechanism. Dio,ysen, another nonpolar molecule. ulso odds reversibly to
V:tska's .:omplcx. but in I his C<ISC the x-v hond is not completely broken. The bond
order of 0 : i.' reduced rmm two to
on.:.
L
L
Cl
><
oc I
CO
L
'1r _.. I
+0!
ct ... I 'o
(15.98)
If X - Y is an clcctrophilic
molecule such as CHJI. oxidative addition
reactions tend to proceed by SN2 mecha.nisms involving two-electron transfer !Eq.
15.99) or via radical, one-electron transfer mechanisms (Eq. I5. 100).
H' .I'H
(L M--C--11
IL.M - -CH)]I- L.MCCH,JI

(15.99)
(15.100)
Other tll.ctors besides a vacant coordination site are important in determining the
tendency for a complex to undergo oxidative addition. The ease: or oxidation (usuaDy
692
lS Organometollic Chemistry
J" to d" with formal loss of two electrons). the relative stability of coordination
number 4 compared to 5 or 6. and the strenglh d new bonds crented (M-X and
M-Y) relative to the bond broken (X - Y) all must be considered. Oxidation of the
mellll is easier for electronrich systems than for electron-poor ones: hence oxidative
addition is more likely for low-valent metals. The ease of oxidation increases from top
to bottom within a triad [Co(l) < Rh(l) < lr(l)) and the tendency toward fivecoordination decreases from left to right across a transition series [Os(O) > 11{1) >
Pt(ll)J.
Oeavage of the H-H bond by transition metal complexes suggests that similar
bonds. In fact it has been known fora
reactions maybe possible with C- Hand
number of years that coordinated triphenylphosphine can undergo intramolecular
cyclometallation.
c-c
Ph,P-n
(Ph1P)1lrCI _...
(15. 101)
H
This reaction is also called orthometallation because it is the onho carbon of the
phenyl group that participates. Although most common with phenyl groups of phosphines or phosphites. examples involving alkyl &fO'IPS are also known.
The recognition that
is capable of nonclassical coordination to a metal, which
may be regarded as an interaction involving incomplete rupcurc of the H-H bond.
w:IS preceded by the discovery that C- H bonds can interact with mellll atoms
complexes.
without bond cleavage. It was first observed that in the structures of
a hydrogen atom attached to a phenyl ring was abnomuilly close to the metal atom.
This was viewed at the time as a form or hydrosen bonding. A subsequent neutron
diffraction study of[f e(7)1 -C.H 11 )jP(OMe)1},)+ revealed a strong C-H Fe inter
Studies of a 'number of polymetallic complexes also provided evidence for C-H

coordination. Particularly notllble was a beautiful NMR study by Calvert and Shapley
of a lriosmium complex. which was shown to exist as an equilibrium mixture of two
strucwres. one of which included a C- H-Os linkage.l4l
1 1
Bailey. N . A.: Jc:nkim, J. M.: M:ll!On. R.: Show. 8 . L J. Clwm. SoK. Clwt. Cowuntm. t965.
237-238. La Plaa>. S. J. ; lb<n. J. A. INNJ:. CNm. tt6S. 4, 7711-711).
Drown. R. K.; Wili_,., J. M.: Scbullz. A. J.: Slucky. 0 . 0 .: Ind. S. D.: Hlltlow. R. L J . Am.
Clrm. Soc. t910. 101, 981-t81.
Calvert. R. 8 .: Shoplcy. J. R. : Sdoullz. A. J.: Williams. J. M.: Suib. 8- L ; SIUCity, 0 . D. J . Am.
CNm. Soc. ma. /00,
:::..::::._
Reocrions of Orgonometallic Complexes
693
Of added significance in this woric was the fac.r that a methyl C-H bond is broken.
which has positive implications for activation of alkanes by transition metals
(page 694).
As more and more examples of a carbon-hydrogen bond acting as a ligand were

confirmed. the term DJ/OStic was coined to describe the interaction. Agostic. as
originally proposed. referred to .. covalent interactions between carbon-hydrogen
groups and transition metal centers in
in which a hydrogen atom is covalently bonded simultaneously to both a carbon atom and to a
transition metal atom ... t..., These interactions. like those of B-H-B and
W-H-W (page 646). are currently described as three-center. two-electron bonds
(see Chapter 14).
As with au other forms of lij:and- me.tal coordination. an agostic interaction
requires that a vacant coordination site be availltble and donation or C- H electron
density to a metal contributes toWllrd satisfaction of the 18electron rule . The cation
[Fe<.,lCMHul[P(0Mel 31J shown above. is an llklectron system if one counts the
C-H bonding pair of elecii'Ons. Structural lip-Qffs iooic:ating the existence or an
agostic interaction include C- H bond lengthening by s-Ul"/. relative to a nonbridging
C-H bond and M-H distances longer than a terminal M- H distance by 10-20"/..
The term agostic has now b.:en
to generally include M-H-Y systems.
in which Y may be B. N. Si. 0. or F. as well as C. The structure ofTiiBH.)1tPMe3):
reveals one bidentate BH; and two monodentate BH; ion$, each of which possesses
one B- H bond attached to tilunium in a side-on. agostic munne.r.''
H'\ __...H ;Mel
H"T"'
[.H, . . . "
H'-Ti
8
H"/ 8-H\
H
'H
PMe 3
The preceding examples ofC- H coordination are all intramolecular in nature. Of

greater interest. especially with commercial goals in mind, are intermolecular reactions involving hydrocarbons. Functionaliz.ing the alkane co nstituents of petroleum
under mild conditions is a major challenge in organometallic chemistry and one thal
,.. Brookllllrt. M.; Green. M. L. H.: Wooa. L.L. l'rol/. /"011. Clw:M. 1911, 16. 1-114. The term
"IOdusp. to <lr.lw tow:ords.lo bold to
ago.<lic is drive<! from I he Grlt wurd u,.,.,.,.;cond
oncselr.
,.., Jcnsc:n. J . A.:
S. R.; Gitol:lnW. G. S. J. Am.
Soc. 1988, 110. 4977-198:!.
has received a great deal of attention during the past decade. tol6 As you know from
courses in organic chemistry. alkanes ure quite unreactive and their inertness is
auributed to high C-H bond energies (lypic:ally about 400 kJ mol). A plausible
sequence Cor functionaliring hydrocarbons begins with coordination or an alkane:
(15.103)
L.M + R - C - H
(15.104)
. . . _ ./R
L.M
......c . . . .
'H
+ reagents - - L. M + hydrocartxln derivatives
(15.105)
Eq. 1.5. 103 shows formation or a three-center , two-electron bond. presumed to be a

first step inC-H activation. The next step (Eq. 1.5. 104) completes the ox.idative
a.Jtlition of the alkane to the metal. The process may be thought or as insertion or the
metal into the C-H bond. Further reaction with o Cunctionalizing reagent gives the
desired organic product (Eq . 1.5. 10.5). An ultimate goal is to accomplish this process
catalytically.
and Hoyano and Graham at
In 198:!. Janowicz and Berl:ffilln al
Alberta' reported the first stable alkane intermolecular oxida tive addition products.
The Berkeley group photolyted I'I'-Me,C5)(Me1P)IrHl with the loss of H2 , while the
with the loss of CO to give highly
Alberta group photolyzed
reactive iridium intermediates which cleave C-H bonds in
115. 111(>)
. fr .
'M<,r j .. H
H
( 15.107)
Cr:lbcroo:. R. H. CMHt. Rt'Y, 15111S. n. 245-269. Shilov.
,., Berpnan. R. G. Scitt t984,11J.
A. E. 1M Artlvolluro uf SoiiVotd 1/ydtDNlrbtHII by TrOtUitiulo Mrtol Comp1.rrs; Rcillel: Dor

drc:cht. 1984. Stoutland. P. 0 .: ll<rJm3n. R. G.: Nolan. S. P.: HolT. C. D. l'ulyi,Jmn t981. 7.
1429-1440. Jones. W. D.: Feher. F. J. J. Am.
$tH". 1911-1. 106. IM0-166J.
" ' J.,.,..;a. A. H.: llaJman. R. G. J . Am. Clwm. $. t91l. 104. J$2-)34.
"" Hoyano. J. K.:
!:
a,m, Soc. t!'l /IH, 372)-)725.
Reac tion of Orgon-tollic Campi
695
Even meJhane. ulllle r the right experimenrnl condiJions. can be activai.W by an

organomelallic complex. This is particularty impartanl nul only because melhane is
one of Jhe mosl abundanl hydrocarbons but also bec:luse irs C-H bond is Jhc:
strongest among lhe alkanes (434 kJ mol- 1) . Success in activating Jhi.s molecule
suggests rhal all alkane acrivation barriers are
The first homogeneous
(solution) reaction between methane and a n Ot"llanometallic complex was reported in
3
1983 and described t he c:xchnnge of ' C H3 for CH3 . t49
f15.J08)
Somewhal similar reacJions with
have also been
II
is likely that neither of these two reaclions proceeds by oxid:llive addition because
luletium and lhoriu m are in high oxidation states in Jhe reacranls.
The activarion of melhane in solulion by an Orllanomerallic complex presents
some experimental difficulties because uny solvenl I hat is likely lo be chosen will be
more reactive than methane. In addilion. insolubility of Jhe comple:\ in liquid melhane
mny precllkle reaction with the pure hydrocarbon . These problems were overcome in
Jhe case of the reaction of CH4 wilh lhe iridium complex of Eq. 15. 106 by taking
advantage of the fuel !hat the desi red hydrillo melhyl complex is thcrmodynamicaJiy
more stable than other hydri<lo ulkyl complexes. The melhyl complex was produced
by ftrSI c.reaJing a hydride cyclohcxyl complex und then allowing it 10 reacl with
methanc. n t
c.
C._H,.
"fll ..C,Me,lt PMc: 1 Jir" _____:.....
lll-C,Mc,I!PMc,llr
/H
no,
'\.cbH 11
'
<
.c,Mc,)(PMc,llr
/H
(15.109)
"-CH 3
The rea.:tanl
in Eq.
the presumed reacrive
is photolyzed .
inlenncllialc that forms when
Another complex 10 whio;h methane. as well as other hydn.x:arbons. will oxidatively add is lhi'ildicyclohcxylpho:.phino)cthonelplatinumllll.
R.
R,
cp::.._
r.:.___
p/
R:
PI + C H , -
/CH.1
PI
(15.1111)
p/
R,
The very electron-rich. two-coordinate. 14-clcctron platinum rcaclanl

nor spec
troscopically observed. bul its
wus inferred from the reaction prollucs.n
Insertion and
Elimination
Oxidative addition reactions lead tO prollucls rhat aPJlCar 10 have had :1 metal atom
inserted into a bond. but the term insertion h:1 s generally been
for reacrions
which do nol involve changes in metal oxidurion slute. These reacJions
enormously important in catalytic cycles (see pngc 701!). Special emphasis in Jhis section
P. L J. ""' Cum. S<H'. t 911J. lOS.

'"' Fcndri.:k. C. N .: Mam . T. J. J. 1\m. Clwm. $<1<'. tft'. 1011.
,.,
'" llcfslnan. R. c. Srinln- 19114. llJ. 11112- <)011,

L<! Hacltctt. M.: Wllilcsides. C. M. } . Am. Cfr<om. Soc. IMI. 110. 1449-1-162. Pbotoly>is of
Fdi2tdppcl, in a xtnunlll'ldhane soluliun aho lead 10 metl-.ne wivoJion. F'ockl. L. D.: George.
A. V. : Messcrle, B. A. J . Cfr<om. Soc.
e-m. 1,1, lll9-tl41 .
696
15 Organometallic Chemislry
will be given to the insertion of carbon monoxide into a metal-carbon bond and to the
inse,nion of ethylene into a metal-hydrogen bond.
A classic example of a CO insertion reaction (called migratory insertion for
reasons to be explained later) is found in the work of Noack and Calderazzo. Ul
( IS.l JJ )
The product of this reaction appears to have formed by insertion of a CO group into an
Mn-CHl bond. The reverse of this reaction is called decarbonylation but may also
be called deinserlion or. more broadly, elimination. Infrared studies with 13CO have
revealed that the reaction actuaUy proceeds by miaration of the methyl ligand rather
than by CO insertion.
0
Dl
c
I
L,.M-CH ---+ L,M- C- CH
I
c
I
L,.M-CH1
(CO insertion)
(15.112)
I
I
c-cH,
---+
L.M-0
(methyl migration)
(15.113)
0 =vacant site
At first glance. these two processes may seem to be indistinguishable . However.
careful consideration of the results of the infrared study will reveal otherwise. The
reaction of uco with CH,M n(COls yields
as the exclusive product. None of the tagged CO is found in the acetyl group. which establishes
that the reaction is not an in1ermolecular insertion. i.e .. no reaction occurs between
gaseous CO and the M-C bond . Furlhermore. none of the I)CO ends up tr.ms to the
acetyl group. This is an extremely import:mt obscrv:uiont>ccausc it establishes that
the CO ligands in the product do not s<:rdmble tn give 11
distrihution. In uther
words,the outcome of the rcnction is kinetically. notlhcrmooynamk:nlly. controlled.
Although this is an important result. it does not allow a firm distinction to be made
between CO insertion and methyl miaration since the product would be the same for
either mechnnism. However, additionnl mechanistic information Clln be gained by
studying the reverse reaction, i.e., decarbonylation of c/.s-(CH,CO)Mn("COJ(C0)4,
because the mechanisms of the two reactions must be the reverse of Cllch other
according to the principle of mici'O:Icopic reversibilily.
Consider the possible products thnt Clln form if dccarbonyll!tion takes place by the
reverse of CO insertion.
Ul Noadc. K. : Cald<nzzo. F. J. Drl!llltnlftf't. Ctlfl. 1967. /0, 111-1().1. Caldcr:ltto. F. AliA"....,, C/um.
Int. EJ. &111. 1971. 16. 299-311 .
697
Reaction of Organometollic Complexes
CH 3
C=O
oc.
1
Mnf
oc.,... I 'co
c
CH
oc, 1
-eo
Mn
CH
oc,_ 1
Mn
(15.114)
oc...- I 'co oc' I 'co

c
c
0
The CO of the acetyl ligand has a choice or four cis positions inlo which it may
shifl, displacing the CO that is alrendy there. One or these sites is occupied by 13CO.
Thus we would predict that 25% or the product would have no 13 CO and the other 75"/o
would have a 13CO ligand cis to the methyl group. Experimentally it is found that 25%
of the product is devoid or tagged CO. 25% of the product has 13CO trons to CH, . and
50% of the product has 13CO cis ro CH3 Therefore CO insertion must be eliminated as
a mechanistic possibility. A methyl migrotion mechanism. however. is consistent with
these experimental rcsuhs.
(15.115)
c- !0
OC
Mn. ':'CO
oc I
c
0
co
._..,
oc ... 1 _,cH,
Mn
Mn
oc...- l 'co Hc' I 'co

c
l
c
0
oc.,, 1 )Jco Hlc,l yeo

0
Mn
oc' I 'co
c
0
The methyl group as it migrates m;,y displace the 13CO ligand to give product
conraining no "CO (25%1: il may displace either of the lw() CO lig;mds 1u.ljacen1 to the
rasged CO to give the product with CH3 cis to I)CO 150"/.J: or it may
the CO
ligand trans 10 the tagged CO to give lhe tr.ms producl 125%1. This result has been
further supporred by carbon-13 NMR.t:<4
The validity of this mechanism has been demonstrated for a number of " CO
insertion" reactions. Thus when chemisls use the term CO insertion. they usually
mean alkyl migration. Several things to keep in mind when considering a reaction of
this type are (I) it involves ligands which are cis to one another, (2) in the course of the
reaction a vacant coordination becomes available, and (3) the reverse reaction cannot
occur unless a ligand is first eliminated.
A chiral metal center, as is foond in a pseudotetrahedrol iron complex with
cyciOpentmlienyl. carbonyl. triphenylphosphine, and ethyl ligands, has also been used
to address the question or alkyl migration versus carbonyl insertion. Inversion of
,. Aood. T. C.; Jensen. J. E.; SIOIIcr, A. J. J. Am.
Soc. t911t . /OJ. 4410-4414.
con!isuration is expected for ethyl misration. but retention is expected for carbonyl
insenion. ts'
(15.116)
?'
f<
R,P I
-.1
(IS. JI7)
When this react ion is carried out in nitromethane, inversion of configuration is

observed. consistent with et hyl migration. In some: solvents both stereochemical
products arc: obtained, which may mean toot both pathways ure operative or th:ll
chiraJ intesrity is lost in the intermediate step.
At this point it is fair 10 ask. what is the driving force for
insen ion'!
Th<!se
involve breaking a metul-curton bond and forrmttion of a c:r
hun-carbon bond. In addition, a bond is formed between the mewl ;mtlthe incomilll!
Lewis hase ICO in the roresoing examples. but frequently 11 phosphin<! \Jr un amine).
The enthalpy chanse. t.H, for the reaction
Mn(CO),CH , +CO - - + Mn(CO),(COCH 3)
( 15. 118)
has been calculated as - .54 :!: 8 kJ

The less
required to break the
M-R bond and the more energy released when the C- C and M-CO bonds are
the more favorable will be the reaction. Since saseous CO is cuptured, it
would be expected that the entropy change would inhibit spontaneity. but c:vc:n so. the
larser negative enthalpy term is dominant. I nscrtions are not always thermodynami-
"' F1oocl, T . C.; Caml>bcl. K. D. J. Am.

L"' Connur, J . A.; Zel'anniMoall3.r, M. T.;
AI Takbin. G .; Skirnor. H. A.
SM. t914. lOll.
J.; El S:>iecl. 1'1. 1.; Sur.di. S.; Canon. R.;

1981. ' lt66-1174.
Reactions of Orgonometollic ComplexH
699
cally favorable, however. as is illustroted by the absence of reaction when Mn(COl,H

is subjected to CO.
Mn(CO)sH
+ CO
Mn(CO),{COH)
(15.119)
The calculated enthalpy change for this reaction is approximately 20 kJ mol- 1 This
result is of considerable
because It suggests thut reduction of CO with a
transition metal hydride. is not n useful route to orannic products (see Fisher-Tropsch
catalysis. page 715).
The organometallic chemistry
actinides. ignored in the early development of
the field. is currently receiving a great deal or attention.tS7 In many instances the
chemistry of this group of elements is unlike that of the transition metals. For
example, it has been shown that a thorium hydride, in contrast to the manganese
hydride shown above. does undergo CO insertion.'"
or
(15. 120)
A driving force for this reaction is the strong interaction of the oxygen of the insert.ed
CO with the thorium atom.
or equal importance to c<U'bonyl
into a metal-carlx>n bon.J is Olefin
insertion inlo a metal-hydrogen bond.
(15.121)
Catalytic hydrogenation and hydroformylat.ion are just two or the many important
processes in which these reactions are ful'klamental (see
71 11. The first
in
the reaction is coordination of the alkene to the metal, followeU by rapid insertion into
the M-H bond. The tr.111sirion state involves a four-center planar structure.
,
/
M- H
I /
c=c ...... -
M -- H ]
,:
/
l/
c-c...... -
/H
-cc/
......
(15.122)
The rcvcf'<c of alkene

p elhnin:otion. rcpn::s.:nts the chief p;tthway for
dc.:ompositit>n ufOttmnsitinn m.:tal :tlkylt.:umplcx
'fhc
h.:gins with
dcinscnion of the :alk)lligatt<l to yickl a metal hydrido .1lkcnc .:omplc!l. "hich then
elim inates the atkene.u The: decomposition process cun be thwurtcd by designing
alkyl complexes in which p elimination is not possible either bccaus.e the lisands have
no hydrogens on carbon atoms fJ to the metal [e.g .. PhCH! CH). or ICH_,)JCCH!J or
the f3 hydrocen is too far from the: mct:llto ullow deinser1ion to occur (e .s .. C=:CH).
Note also that fJ elimination cannot toke place unless there is a vacant site for
"'M<lli<s. T. J .: Slroitw;.,..,r, A .. Jr. In T1t.o Chr,.,iII'J r>{tlrr
EMntrnt>; Kal7., J . J.; Sc;oborJ.
G. T.: Mur>s. L. R.. Ells.:

and Hall: New Yorlc. 19H6. Marb. T. J. M<'. Cltrm. Rrs.
1992. 15. S7-6.S.
""F_.. P. J.: Mvloy. K. G.; M;atU. T. J. J . AJH. CJu...,, Sue. 1911. /OJ.
,, Crass. R. J. In Thr Clrr...Ut'? rl/ "' MrtaJ..Curbmo B,..J: Hanley. F. R.; Pal:li. S .. Eds.: Wiley.
New Yorlc, 19S5.
700
hydrogen to occupy in the deinsertion step. Thus IS-electron complexes with ligands
that remain :lllached to the central metal. such as the dicarbonylcyclopentadienylethylironUII complex shown below. are kinetically inert with respect to fJ elimination.
Nucleophilic and
Electrophilic Attack
of Coordinated
Ligands
Org;snometallic complexes frequently are susceptible to nucleophilic attack by an

external reagent. In some instances the attack takes place on the metal center (see
substitution reactions. page 686). while in others it occurs on a bound liGand. Already
in this chapter we have seen many instances in which coordinated carbon monoxide
undergoes nucleophilic auack. Examples include reactions with H- to produce a
formyl complex !Eq. 15.19). with R - to form an acyl complex (Eq . 15.49). and with
OH - to give a hydroxycarbonyl complex (Eq. 15.211.
(15.123)
We have also observed that the carbon atom or a Fischer carbene is subject to reaction
with nucleophiles (Eq . 15.52).
Coordinated unsaturated hydrocarbons are particularly susceptible to nucleophilic alluck even though as free organic molecules they tend to resist such reactions
becuuse they arc relatively electron rich. Upon coordination. they yield some electron
density to the metal and thereby lose some resistance to reaction with nucleophiles. A
metal fr.lllment with good 1Tacceptingligands and/or a positive charge (i.e . one thllt is
more electroneg-.uive) will therefore be an especiaDy good candidate for activating an
unsaturated hydrocarbon toward nucleophilic attack. Of course not all coordinated
unsaturated hydrocarbons are equally reactive. The following order or nucleophilic
susceptibility in 18-dectron cationic complexes has been established. 1M
The usefulness of such a series is twofold: (I) If two different uOSllturnted ligands are
fount! in the same complex. one can predict which ligand will react. and (2) it is
possible to estimate how activating a metal fragment must be in order to cause a
reaction to occur. Notice that hydrocarbons of even hapticity are more reactive than
those with odd hapticity. In addition. acyclic ligands are more reactive than cyclic
ones.
Reactions illustr:.ting nucleophilic attack on coordinated olefins and allyls are
shown in Eqs. 15.124 and 15.125.
'""Davies. S . G.; Green. M. L. H. : Mingos. D. M. P.

IV7ll. J4. 3047-311n. Collman,
J. P.: Hegedus. L . S. : Nonon. J. R.: Finke. R. 0.
tJm/
M-'al CMmill"' 2nd col.:
Science Books: Mill Valley. CA. 1987; p 409. Crablr.,.,,
R. H.
ChrmiJtry of
Tran.sillon
Wiley: New York. 198H: p 148.
Reactions ol Organ-etallic Complexes
701
(15.124)
N<Jte that in the second reaction the metal atom underl:(les a formal reduction.
As is evir.Jent in the above reactivity series. the cyclopentadicnyl group Is one or
the least reactive lig;md s toW<lrd nucleophiles. As a result. it is widely used in
Ol]lanometallic chemistry as a stabilizing ligand which will remain unreactive. In
Eq . 15. 124 the Cp ligand remains a spectator while the alkene reacts wilh the incoming
nucleophile.
The or-ganic chemistry of benzene is dom inated by electrophilic substitution
reactions. but as a coordinated
it u nderi:IJCS nucleophilic substitution. 'This
dramatic chunge in chemical bchuvior is a good example or the powerful Influence
coordination can huvc on the chemistry of u molecule 01nd is illustruted in the following
functionaliz:ttion of benzene. Ull
(15. 126)
Oxitlalion or the complex with
the derivative of benzene.
(15.127)
'"' Scmmclhadc. M.
Yamashita. A.
0 . R.:
J. L ; Huni:son. J. J.; Tllc:bl.r.ononth. Y.: Wultr. W.:
191t. 11. 39S7- l96S.
The net result is that benzene has undergone a substitution reaction that is not possible
for the free molecule.
Although the coordinated cyclopentadienyl group resists nucleophilic attack. it
does react with electrophiles. Ferrocene resembles free benzene in that it reacts with
many electrophilic reagents, but it does so at an even faster rate than benzene. The
a romatic character offerroccne was recognized soon after the complex was identified
and has led to a rich liter ature. Among the numerous reactions that have been studied
is acylation in the presence of a Friede i-Crnfts catalyst.
AJCI,
C- Cii,
C-Cii,
t
Fe
I
Fe
(15.128)
i
The AI03 catalyst reacts with CH 3COCI to generate the electrophilc, CH3c+=O.
CH3 COCI + AICI3 ---+ CH 3 C= o
+ AJO;
(15.129)
The reaction of acetic anhydride with phosphoric acid will generate the same electrophile and offers the
that only the monoacyl product results. Acylation of
the first ring deactivates the second and the concentration of CH 3C+ =0 from the
acid reaction is too small to produce the diacyl procluct.
A second example of the reactivity of the ferrocene rinp is their condensation
with formaldehyde and amines (the Mannich condensation):
Fe(175-C5 H 5h
+ CH10 +
<l1'-C5 H5 )Fe(,1-C,H 4CH1 NMe2 )
(15. 130)
Fe rrocene thus resembles the more reactive thiophene and phenol rather than benz.ene
which does not undergo Mannich condensation.
Other reactions typical of aromatic systems. such as nitr.ltiun aoo bromin;ttiun.
arc not fc<tsible with metallocenes because of their sensitivity to oxidation.'"! How
ever. mllny of the derivatives that would be prOI.Iuced in these types of reactions can
be made indirectly by means of another reaction typical of aromatic systems: metall a
lion. J ust as phenyll ithium can be obtained from benzene, analogous ferrocene compounds can be prepared:
"" Ferroccne loses 111 elec:trOil ruther rctucwuly since b involves dionlplifli an IS&clrDllocc:nium ion. losina the IIJih o.nd
llfllibonllina electron. Nicltelooene loses one of its two MCiboo<lirw elect runs 10 rorm the rdalivcly
.... table nickdoc:aWum ion.
""'Y
lteoctions of OrSJonometalllc Complexes
703
(JS.IJl)
These lithio deriva1ives are usefu l intermediates in the synthesis of various femx:enyl
derivatives. Some typical reactions are:
(15.132)
CJ5.133)
Corbonylo te Anions
as Nucleophiles
C.orbtm}Lloc complexes have m:my

synthetic upplic.ations. Typical reactions
involve nucleophilic auack of tho: metal :onion llll u flll\ilive cemer lallem>ltively
on the met all . The
uf mcml alkyl com
viewed :os an clcctrllphilic
plcx.:s ha.'> been reli:rred to earlier tEqs. IS.-16 und IS.-171. 01her examples include:
RCX
+ (Co(C0)4 ) -
Mn(CO),Br
+ [Mn(CO),r
RCCo(CO). + x-
Mnl(C0), 0
(]5.134)
+ Br-
(15.135)
All housh the reaction in Eq. IS. IJS is of lillie importance in the manufacture of
Mn!IC01 10 (lhe
typically :1re
from the dimansanesc complex). it
a
and useful mclho.J of formin11 metal- metal bontls thill can be
applied to
in which the metals are different:
704
lS Org..,omeJoUic ChemKtry
Mn(CO),Br + (Re(CO)sr ---+ (OC),MnRe(C0)5 + Br-
(15.136)
+ 2[Mn(C0)5 ]- ---+ (0C)5 MnHgMn(CQ)5 + go;PhSn0 3 + 3(Co(C0)4 ] - ---+ PhSn(Co(C0)4 ] 3 + 30(Pb,P)zNi02 + 2(Co(CO).r ---+
(15.137)
HgS04
(15.138)
+ 2CIU5.139)
Applications of carbonylate reactions in organic synthesis are numerous. Particularly

noteworthy are schemes involving tetrncarbonylferrate{ -II) (referred to as Collmans
reagent). Which can be isolated as a sodium salt,
I..S dioxane, and is
commercially available. The highly nucleophilic (Fe{C0)4)2 - reacts readily with alkyl
halides to yield alkyl iron carbonylates:
RX + (Fe(C0)4 ] 2 -
----+
(RFe(C0)4] -
+ x-
(15.140)
These: alkyl complexes do nOI undergo fJ elimination (the stable IS-electron complex
does not provide the necessary vacant coordination site) and optically active R groups
do not undergo racemization. Migratory insertion reactions (page 695) do occur in the
presence of Ph3 P or CO to give the corresponding acyl complexes.
(15.141)
Although the alkyl and acyl products shown in Eqs. I.S. I40 and 15. 141 have been
isolated ami characterized. they are frequently allowed to simply form as intermediates. which are then treated directly to produce aldehydes. carboxylic acids. ketones.
esters. or amides.
H'
RCHO
(15.142)
RCOOH
(15.143)
RCR'
(15.144)
II
ll
IRCFeiCO>JLr
(15.145)
0
x,
RCX
RCOOH
(15.146)
RCOOR'
(15.147)
II
Thus Collman's reagent functions much like a Grignard reagent in its ability to convert
alkyl halides into a wide variety of organic compounds.
Cotolysis by O,.gonometollic C0111p0<1nda
705
A rich chemistry husulso developed for the chromium dianion. [Cr{C01$f- . Ill} The
expc<:ted displacement of Cl- occurs when this reagent reacts with nn acid chloride:
0
[Cr(CQ)sJl-
D
D
Rca - - (RCCr(COI,J-
Cl -
(15.148)
The acylate complex may be alklyated directly to give an alkoxycarbene or the same
end may be achieved by acetylation followed by alcoholysis:
(15.149)
OOH
(15.150)
The
transi tion metal carbenes have been used to synthesize a wide variety of
organic compounds such as furanocoumurins"... pyrroles. IllS and p.lactams. 1""
Catalysis by
Organometallic
Compounds16 7
A thermodynamically fuvor.1ble reacaion may be slow at modest temperatures and

therefore not of value for synthesis. Increasing the temperature of the reaction may
significantly acoelerate its rate. but providing the energy to do so is expensive and
higher temperatures m:lY induce competing sio.le reactions that will greatly reduce
product yields . A more attractive approoch to
the rate of a reaction is to use
a catalyst .
are classified as lwiiWJifll<'tllls if they are
in the reaction
medium and IJrtt:rOJI<'II<'tms if they are insoluble. Each type has
:ulvantajleS and
disadvantages. Heter0eneous
are e:1sily separated from the reaction products ta very positive feature! hut tend tu require r.1thcr his h
and pressures anti frequently lc:ld tu mix tures of protlucts. i.e: .. they huve low selectivity.
'" Sc:mmdllack. M. F.; La:. G. R.

1987,6. 11139- 11144.
'"'Wulff. W. D.; McCollum. J. S.: Kunnc. F.-A. J . Am.
SH:'. 19111. 1/0. Nl9-79J.I. OOIZ.
K. H. AnxMo. Ch<m. /111. EJ. &/((. 19114. lJ.
""Ongisic.h . V.; Mutr.ty. C. K.;
8 . P.: WuNT. W. 0 .; Yq. D. C. J . Am. Ch<m. Su. t 9'JO.
111. tlSt-tm.
'"" Hq:cdus. L. S.: de Week. G.; D'An<ln:u. S. J. Am.
St><. t1168, 110. 21:!2-2126.
For men: lhorooah .!iocus.ion> of 1hio lopic. see Collmon, J. P.: He..,llus, L. S.: Nor10n. J. R.;
Finke. R. G. Prinr ipln """ ...pp/i<'athHU ufOrXIIIIOlrtmzititJII Mrta/ C/ltllll.rry. 21>11 cd.;
sily Sc:icnce Books: MiU Volley. CA. llltl7: Croturce, R. L. Prlnclplrs uf
istry;
waey;
New Yotk 191!8; l.llkchnn.
c. M.
a,..,_
TTIJIUitHHI M.to/ Or7:untHtorta/l{('

Chn.Wry; BrQ<>ks/Cole; Monterey, CA IIIIlS: Panllall, G. W. HtHI!Of.<r-ns CuuJysls; Wdcy;
New York. 111110: Bood. G. C. Htterr1(ni<'U<IS Cutfllyns. 211<1 ed.; Clnrtntlon Prru: Oxford, 111t11.
706
1 S Organometallic Chemistry
Homogeneous catalysts must be separated from the product (a negative feature) but
operate at low temperatures and pressures (a very positive aspect), and usually give
good selectivity (another very positive aspect).
Many important chemicals are produced commercially by reactions which are
catalyzed by organometallic compounds and this fact provides one of the motivating
forces for studying organometallic chemistry. Much of the focus in this section will be
on homogeneous catalysis because solution reactions are better understood than are
the surface reactions of heterogeneous systems. It is also easier to modify an
organometallic compound and evaluate the effects of the modification than it is to alter
and study a surface.
Alkene
Hydrogenation
Although the reaction of hydrogen gas with ethylene is thermodynamically favorable,

it does not take place at room temperature and pressure.
H 1 C=CH 1
+ H1
---+ H 3 C- CH 3
(JS. ISJ)
AH 0 = -136 kJ mol- 1 Aff = -101 kJ mort

However. in the presence of metallic nickel, copper, palladium. or platinum. the
reaction is fast and complete. The metal may be deposited on an inert solid support
such as alumina or calcium carbonate, but the reaction is with the metal surface and
therefore is heterogeneously catalyzed.
The first effective homogeneous catalyst to be discovered for hydrogenation was
the S(juare planar 16-electron .f' complex chlorotris(triphenylphosphine)rhodiulll(l).
(Ph,I'IJRhCI (Fig. IS .47), which is known as Wilkinson's catalyst. In Chapter II we
saw that this geometry and electron configuration are an especially favorable combination. These species also have wide possibilities for oxidative addition Ipage 689). They
can become live-coordinate through simple addition of a ligand or six-coordinate
through addition combined with oxidation. In either case they become isoelectronic
with the next noble gas. i.e. , they achieve an IS-electron valence shell configuration. It
Fig. 15.47 Structure or

Wilkinson 's catatyt.
(l'ti 1PhPhCI. !From Jardine.
f . H. Prtl.'l- lnrwg. Cltt'm.
t9111 . ]8. 63. ReprO<luced
with pcnnission.l
Catalysis by Organometallic Compounds
707
is not surprising then that 16-electron square planar complexes have been regarded as
very attractive catalyst candid:ltes on the premise that they may oxidatively add two
reactant molecules and thereby enhance their reactivity.
Wilkinson's catalyst is thought to behave as follows: In solution one of the
This tricoordinate complex is
phosphine ligands dissoci3tes. leaving
very reactive and has not as yet been isolated, but the closely related [(Pfl:IPhRht.
which could form from the dissociation of 3 chloride ion from Wilkinson's catalyst has
been swdied and found to have an unusual structure (fig. IS.48}. Unlike most threecoordinate complexes (Olapter 12}. it is more T-shaped than triangular. The evidence
for dissociation of a Ph,P ligand from (Ph3P)3RhCI is indirect but persuasive: ( 1} For
complexes with less sterically hindered phosphines (e.g., Et 3P), the catalytic effect
disappears-apparently steric repulsion forcing dissociation is necessary; and {2) with
the corresponding iridium complex in which the metal-phosphorus bond is stronger,
no dissociation takes place and no catalysis is observed.
To return to the catalysis. the (Ph,P),RhO molecule. possibly solvated, can
undergo oxid:ltive addition of a molecule "of hydrogen. An alkene can then coordinate
and react with a coordinated hydrogen lig3nd to form an alkyl group. This reaction will
result from a migration of 3 hydrosen from the metal to a carbon in the coordinated
all of the moving. this reaction is
alkene. Although the hydrogen atom does
often called un alkene insertion reaction (page 699).
The reactions involve<.! in hy<.lrosenation with Wilkinson's catalyst thus can be
represente<.l as follows CL a Ph,P. S = solvent molecule).l''"
L
L-Rh-::::_L + S
Cl
/s
L-Rh-L+ L
/
Cl
(15.152)
Fig. 15.48 Stcreovicw of the structure of the !(Ph,P))Rh( cation. st>owing the plano.r.
approximutcly Thaped coordination abolll the rt>odium otom. Note the unusual rnllRner in
which the phe.nyl ring at the lower right is drnwn toward the rhodium atom. !From YllfCd.
Y. W.: Miles, S. L. : Bnu. R.: Reed, C. A. J. Am. C/wn. Soc-. 1977,99, 7071>-71178.
Rcpmduccd with
,,. For a more detailed mcchanisJic view. sec Halpern. J. /nt>r/1. Chim. AcYtl tll8t. 50. ll-19. It has
bo.'en ucgcoted that the phlo<pl\inc lig:llllls may be ci< in the oclllhcdral inu:rmcdiulu. Brown,
J . M.; 1.\Jcy. A. R. J. Cbtm. Snc., C/tttn. Cumnuw. 1984. 914-!IIS.
708
_....s
1 _....H
L-Rh-L+H -
_....
L-Rh-L
(15.153)
_....I
ca
(15.154)
Rllleodetermining
Slep
(15.155)
I_....L
0-Rh
I'l
+S-
(15.156}
Cl
I _....H
l-Rh-L
s_.... I
(15.157)
Ethylene is commonly chosen to illusuate homogeneoLtS hyllrogenution with

Wilkinson's catalyst. but the process is actually v.:ry
with this alkene. The
explanation lies with the formation of a stable rhollium ethylene
which does
not readily undergo reaction with H,. Ethylene competes .:ITcctively with the solvent
when triphenylphosphine dissociates from
for the vacant coordination site
Wilkinson's catalyst and thus serves as an inhibitor to hydr"'--enation.
(15. 158)
Tolman Catalytic
Loops169
A reaction involing a true catalyst can always be represented by a closed loop. Thus
we may combine Eqs. 15.152- 15. 157 into a continuous cycle with the various catalytic
species forming the main body of the loop and reactants and products entering an<l
leaving the loop at appropriate pl:lc.e s:
"'"Tt*mn. C. A. C1tfflt. S. Rft. t972. I. JJ7.)S).
Cotolysis by Orv..,o101etollic Compou11ds
709
( 15. 159)
l!ydr..... .,..,.._
Synthesis Gos170
The history of org-.mic indu!'<lrial chemistry con be orsnni7.ed around the rel:ltive
of the organic feedstocks used durin& u particul:lr em.111 The years
1910-19SO can be characterized us the "acetylene period" since reatlily av-o1ilable.
highly reactive, but rather expensive acetylene was employed. From 19SO to the
present. alkenes have predominated. It now
that alkenes in turn will be
replaced by synthesis
tH:JCO)
the raw material of choice, and we shall enter
the era of one-carbon fectlstockN. The evolution of homogeneous catalysis for industrial use has been extended 10 ever cheaper
less reactive fccdstocl:s. Synthesis
g.1srn can be produced from .:oat ;md was one of the reasons interest in coal rose
marketlly durinr;;the oil embargos of the 1'.17Us. Emhusillsm towurd coal as a resource
waxes ;md wanes as the price Ill' pctmlcum rbcs and ralls .
The li rst H./CO mixture h> be of cummcr.:i;al impon:mcc w;ts obtained from the
uction of steam- on r<.'tl-hot coke and . because of
<>rigjn. became kO()wn as wall!r
J:tl.f:
(15.160)
In the 19th-century days of gas lamps. water ga.s was frequently used for domestic
purposes. a practice fraught with danger because of the extreme toxicity of carbon
monoxide (see Cf;mpter 19). T he rJtio of hydrosen to C'Jrbon monoxide in water gas
'"'Sheldon. 1! . A. CJtr,..irlllfrom Sytlllttsu C.U : D. RcM!c:t: Ootdtttht. I'ISl.

"' P:J.nh&>ll. G. W. llomolt<'rW'IHS CIIUtysis-. Wiley: New YOtk. t9ICO: p !23.
m The rum synxa is a brood t"fm used to cover vuriwlc
of curbull monoxide: 3no.l hydroccn.
can be altered with the

slti/t rtoctinn _which cnn be catalyzed by a variety of
heterogeneous and homogeneous catalysts:
(15. 161)
There are several reasons for wishing to aller the hydrogen concentration. First,
hydrogen is a more versatile industrial chemical than water gas. Second, small organic
molecules tend to have roughly three to four times as many hydrogen atoms as carbon
atoms. so if the H 2/ CO mole ratio can be changed to about two, a good feedstock is
obtained.
Commercially, the water- gas shift reaction is usually carried out over Fe30 4 .17l
However. cum:nt interest centers oo homogeneous catalysts. Metal carbonyl comand (Rulbpy)z(CO)CW are effective nnd
plexes such as (H Fe(COJ-.
although all the mechanisms have not been worked out completely, the reactions may
be viewed in general terms as beginning with a nucleophilic auack on coordinated
carbon monoxide:
M-
ro
HO
M-C=O -
M- c - o --...:. (M- Hr
(15.162)
OH
The hydridic hydrogen can then attack water:
[M-H]-
+ H1 0
M +OW
+ H1
(15.163)
Alternatively (nnd equivalently) a

mole<:ule c-.m attack in Eq . 15. 162 (freeing an
H ion) followed by attack of a proton on the hydridic ion in Eq. 15. 163. A scheme: for
can be presented as:
the react ion catalyzed by
(Rul: (CO)CW
This particular cycle is significant because: ul l or the: key intermediates have been
isolated. 174 Substitution of H2 0 for a- in (Ru(bpyl:(COlCW gives (Rulbpy),:(CO}(H:O>f which exists in equilibrium with (Rul bpy).:(CO)(OHW'. Carbon monoxwe
m Ford. P.C . .ike. Clrt m. Rts . 1911. 14, l t-)7.
P Ishida. H.: Tanaka, K.; Morimolo. M.; Tuab. T. ()rxafOUmtt(ll/ks 11186. J, n4-nJ.
Cotolyas by O.,.onolllelollic C0111pounds
711
displaces water to give [Ru(bpy)1(C011f which undergoes nucleophilic attack to

form a hydroxycarbonyl complex. Decarbonylation occurs with hydride formation
followed by liberation of hydrogen gas and reformation of the c:.talyst.
1lle preferred route to synthesis gas currently is by reforming methane (principal
component of natural gas):
(15.165)
Whatever the source of synthesis gas, it is the starting point for many industrial
chemicals. Some examples to be discussed are the hydroformylation process for
converting alkenes to aldehydes and
the "Monsanto process for the production of acetic acid from methanol, the synthesis of meth:lnol from methane, and the
preparation of gasoline by the Mobil and Fischer-Tropsch methods.
Hydroformylotion175
The reaction of :In alkene with carbon monoxide and hydrogen , catalyzed by cobalt or
rhodium salts. to form an aldehyde is called hydrnfnnn.vlatioll lor sometimes the oxo
procrss):
+ 2CO + H1
Co,ICOI.
R H 2CH1CHO
+ RCHl!CHOICHJ
( 15.166)
II was discovered by Roelen in 1938 and
the oldest and largest volume catalytic

reaction of :llkenes, with the conversion of propylene to butyralc.lehyde being the most
important. About S million tons of aldehydes and aldehyde derivatives !mostly alcohols) are Jli"OOUCed aMually making the process the most important industrial synthesis using a metal carbonyl complex as a catalyst.' "' 1lle name hydroformylation
arises from the fact thod in a formal sense a hydrogen atom and a formyl group :Ire
added across a double bond. 1lle net result of the process is extension of the carbon
chain by one a1l<l intro<luctio n of oxygen into the molecule.
The most widely accepted mechanism for the catalytic cycle is the following one
proposed by Heck and Breslow: m
ICOl 1Co C-CH,CH,R
\
1" Prudl. R. L J. CMm. f:Jur. 1986. 6J.
"" Orchin. M. A. a...... Ru. 1981. 14, !SY-266.

on Heck. R. F. : Bmlow, D. S. J. Am. CMm. Soc. 11'61, 41.
(15.167)
716
15 Orgoft....,etollic Chemistry
Alcohols and alkenes arc also primary

and arc not shown in the simplified
Eq. 15. 11!2. The overall reaction is complicated and, as u result, its mechanism has
TilC reaction may be viewed as the
been the subject of considerable
reductive polymerization of ca.-bon monoxide, with molecular hydrogen as the reduc
ing agent. A variety of heterogeneous catalysts. such as
iron and cobalt on
alumina. have been used . It is believed that carbon monoxide dissociates on the
camlytic surface to give carbides and that these are in turn hydrogenated to give
surface carbenes: lll'i
C
0
CH,
,..----- - - - . co ,_..._.1_ __..1__, "

.___ _ ___,I - - I
I _._.
1\ .
'------J' + H20
(15.183)
Carbene insenion into a metal-hydrogen bond gives a methyl group that can undergo
carbene insertion in a propagating manner:
CH,
/\ -
H
I
CH,
1\ -
CH2
CH3
I\
CH 2
1\
CH1
I\
'---------11- ._1____ _ __,I - CH3
CH,
CH,
I -
1\etc.
(15.184)
Although it is alw-.1ys somewhru risky to draw conclusions about surface reactions

from solution experiments. a number of such studies suppt the carbide/carbene
mechanistic proposal. A model compound for the carbide proposal is a butterfly
cluster formed from an unusual six-coordinate carbide: 1911
Fe
101
C"
(15.185)
Fe
Fe
Fe
Fc4C(C0)1;
The exposed carbide carbon reacts successively with carbon monoxide and
methyl alcohol:
'"" Rofer-OePoorler. C. K . Clrtm. R<v. 1911,81. 447-474. Htm1111nn. W. A. AI!!(..... Clrt'to.

Ens:t. t982. 21. 117-tlO.
EJ.
' "" Br:l<ly. R. C. Ill: Pcuil. R. J . Am. Clrrm. Soc. 1980. 101. 6t8t-6182.
"'" Br:l<Jcy. J. S. ; Anodl. G. 8 .; ucnowicz. M. E.; HiM. E. W. J . Am. C11tm. S.... 198t. 101.
--.mo.
Cotolpis by
c-pounds
717
co
Ft
Ft
(15. 186)
followed by hydrogenat.ion to yield methyl acetate. Note that a carbon-carbon bond is

formed in this reaaion. The net synthesis produces an organic oxygenate from
synthesis gas, which may also occur in the Fi.s cher-Tropsch reaction.
Support for the propgsalion step of the Fischer-Tropsch reacrion is provic.led by
the homogeneous reaction: tn
CH
I )
H
CH
H'c/ -'
I...-'-
Rh--Rh
CH,
'@
us.um
The bridging carllenes of the bimeta" ic complex. which parnllel the swfac:e Cll'benes
of the Fischer- Tropsch cutalyst. are involved in
bund formution.
Both the Fischer- Tropsch reaction aml the Mobil process enable one to .:on vert
synthesis ll"" into hydrocarbuns. Since synthesis sas may be obtained from coal. we
have in c:flect a meuns of convertintt coal to ga.wline. Germany moved its
Korps in World War II with synlhetio; fuels made (rllm the
reaction .
and improved technological d..:velopmenls have enhuncccJ the ulln1ctiveness uf the
process. South African Synthetic Oil
CSASOLl currcmly operates s..:vernl
modern Fischer-Tropsch plants. Many organometallic chemist.s refer to both the
Fischer-Tropsch and Mobil processes
'"political processes'"avz because they are
heavily subsidized by countries that lind it important to be independent of foreign oil.
c-c
l.OOC. K.; Andrew:<. D. Ci.: Morwo. B. E.: Maillis. P. M. J.
S"<:. Ch..,..
t98t.
1109-l! IO.
,., Collmun. J . P.:
L S.; Nonon. J. R.; Finke. R. G. Prinriplvx mrJ l41'fllirativns t1[

Org.,utrtlll.<ltkm M<'tul Clrrmillry, Znd cd.; Uruvcrsity Science
Mill Vnllcy. CA. tl/87;
p620.
718
1 5 Organometallic Chemistry
Z.iegler-Notta
Catalysis 193
One of the great discoveries of organometallic chemistry was the catalyzed polymeriz.. tion of alkenes at atmospheric pressure and ambient tempernture. Vast quantities of polyerhylene and polypropylene (over IS million tons annually) are made by
Ziegler- Natta catalysis. Ziegler and Naua received the Nobel prize in chemistry in
1963. and the importance of rheir work in stimulating interest in organometallic
chemistry should not be underestimated.
The Ziegler-Natta catalyst, which is heterogeneous. is made by treating litanium
tetrachloride with triethylaluminum to form a fibrous material that is partially alkylated (Et,AICI is used as a cocatalyst). Third generation catalysts (introduced about
19801 use- a Mg0 2 support for the TIQ4 The titanium does not have a filled coordination sphere and acts like a Lewis acid, accepting ethylene or propylene as another
ligand . The reaction is thought to proceed somewhal after the manner of Wilkinson's
catalysts discussed above except that the alkyl group (instead of a hydrogen atom)
migrotes 10 the alkene:
H2CTCH2
- Ti:::_CH, -CH
'I
c,,.,
- Ti:::_CH,-CH -
'I
(15.188)
CH 2 -CH,
I ___
,-I
-TI
I ,
CH-CH
The heterogeneous nature of the reaction makes it a difficult one to study. but it has
been ITIOileled homogeneously wirh a lutetium complex which undergoes oligomerizmion: IY
,
C>r-McsCshluCHJ --'---...;.,.
I'I'
('!5-Me 5C5 12 luCH 2C HCCH3 lC H2CHCCH 3 12
Immobilized
Homogeneous
Cotolysts
(15.1119)
Since homogeneous catalysts tend to offer fast reaction with high selectivity an.!
heterogeneous catalysts offer ease of separation. it is not surprising that effons have
been made to combine rhe adYllnrageous properties of both. One way to effect this
combimuion is to altach the "homogeneous" catalysts to the surf'-.lce of a polymer
such as polystyrene. Wilkinson's catalyst. for example. can be !reared as follows: 1''l
,., Caadatt . 8 . L. J.
EJm. 19!16. 6J. 191- IIJS.
'"" Walson. P. L. J. Am. C11tm. s..-. t911.!. IIH. J37- JJ9.

Grubbs. R. H.
19n. 7. 5!2-518.
Catalyllia by Organometallic Co,pounds
+
CH
I
+.
-n
719
+
CH,
I
-n-- .
CH----yr- L
-In
+
CH,
I -
(15. 190)
Ph PPh.
I '
CH- o - P-Rh-CI
+.
A Photodehydrogenotion Cotolyst
("Platinum Pop")
Ph PPh,
We have seen in Chapter II that the

square planar conligur:uion is pan icular1y
stable because four of the mostly metal nJ molecular orbitals are stabilized relative to
the J_..:_,..--<lerived orbitaJ.IIlb Three of the four o rbilals (J.,. J: aoo d_.:l may panicipate in metal-lig-.md .r bonding. but to a first approximation. the J.: orbital .Joes 1101
interact with any other orbitals in an isolated square planar com.ple., . "" Suppose.
however. we configure the complex so that the J.:. is forr:rJ into imerolCtion. By
bridging tll"n square planar complexes. the two
are forced to lie parallel (faceto-fi;ce) at a fixed distance;
but if we .:urcfully dcsisn the

to
nr ligamls that
have !x"Cn .:xtensivdy sttlllicJ an: b<.t:yanill.:s
pynph<J,phill! . Cnnsitler. f.,r
.:xamplc. isoq:mitlc lisan.Js of the typ.::
Many possible ligands could span th.:
we c:tn cnntrolthis metal- mclal
R.C- N::=C-+
/
(\H1J.
R1 C-N::=C-+
, ... In lhc simph: cry<l>l fickl thcory.lheJ,.: ,1otl>i1ol i< very

rcpclk-.1 :lllll.:mp1y: on MOT. il
inlcrucll ..;th lhc -x. :-. -.v lis>n<l IU rurm
b<>IMiint:
<mply.
uoo&)y antibondint: MO.
rw Since die .J,: ort>il:ll dots have some: clcclron dcnshy in I he X1 plunc:.thcfc is ,..,.... lnler.JCtion ,.;1h
Jhe X umJ y tij;31l<b.
720
15 O,.goOflle tallic Chemistry
(where - represents the lone pair on the ligating carbon atom). l911 Note that the
system must be linear throughout the C- NI!IC- M system. We thus have four
groups on each metal spaced by (CH:)n brid&es which may vary in
depending upon n .
A second type of bidemate liaand holding the two metal atoms close together Is
pyrophosphite. II forms from diphosphorous ("pyrophosphorous'') acid and. because
of the P- 0 -P linkage, is often abbreviated "'pop":
II
o
II
Pt
P=O
Pt
P =O
'OH
.......oH
4 "0 - P-0-P-0 " tr.cl,r
1J
:::;0
(15.191)
Coordination of the pyrophosphite occurs through the phosphorus, which is preferred

over the harder oxygen by the soft Pt(ll) ion. Thus there is a tau tomeric relationship
analogous to thar in phosphorous acid:
H - P-OH
OH
OH
:P- OH
(15.192)
OH
The formulation of the teltakis(J.<diphosphito)diplatinate(ll) ion is thus ( Pt 2(pop).f1Fig. 15.491. ' 99 The metal in these complexes is roeally a cf' species such as Jr or
van der Waals radii of these metals (Table 8. 1) are about 3SO pm. so we
should expect metal-metal interaction to begin at about this distance and become
mo re significant as the distance decreases. What will this interaction consist of?
IS.SO illustrates the energy levels of a d 1 square planar complex together with
Fig. 15.49 Crystal

s1ruc1ure ot K..ll'lzll'
P10,H,)4) . (From
Roundhill, D. M.: Gr.:ay,
H. 8.: Che. CM. Me.
Clltm.
t989, 12.
Ss-61. Reproduced with
permission. !
..... ComplcJces or these lipnds have been Cllensivcty SludO:d by Gray Mel cowool<ers. See. ror
example. Maverick, A. W. : Smilh, T . P.: Mnveric:lt. E. F.: Or.oy. H. B. ln<Ns:. Clrrm. tn1.16.
4)36-4341.
M This ion was firsl oblllincd (rom the l"eXIion of
ICir.IChtorop.Jinalc(llt with ....,..en
nOd. The ion cjves an inlmK arcen ll.wnittcsa:n when Sllbj<cd 10 tiaht. Zlpp.
R_... tm. M. 47-&l. The ion undersocs cWd;tlion in I he presmoc 0( air and
A. P. Coot"d.
chloride ion IChe, C.M.: Buller. L. G .: On.wll""-. P. J.; Gray. H. B. lnorg. Chrm . t935. 14.
Catalysis by Orgonomeiallic Compounds
-LUMO
721
Fig. 15.50 Lefl and right:

Ene<JY diogrnms for ML..
dl SQIIarc plonar complexes
showina four filled d
orbilals, one empty d
orbital. and one empty p
orbital on each. Center:
Interaction t he metal d,:
and p, orbitals of two ML
or
units. Other interactions

have been omincd from the
diagram.
the interaction of two filled d..: and two empty p . ortlimls on adjacent metal atoms)OQ
As the distance between the iwo metal atoms decreases. the orbitals alons the :axis
will internet more st rongly with each other. For both the d.: ortlitals and the p.
ortlitals. this will give rise to a bonding and an antibonding
Since the
ortlilal gives rise to the HOMO and the p . orbital to the LUMO. this will decrease the
HOMQ-LUMO gap with interesting co,;-sequences (see below). More important for
the present discussion. the increase in energy for the HOMO will destabilize the
molecule and make it more reactive. Another way of looking at this enhnnced reactivity is to say that if the two electrons were re moved from the amibonding a::,,
HOMO, t here would be an M-M single bond. stabilizing the molecule. One way to
remove the two HOMO electrons without costing energy-indeed. by p roviding
further energy that actually drives the reaction-is to form two new bonds with them :
d_;
RX
(15.193)
::on Roundhill. 0 . M.; Gr:>y. H. 8.: Chc. C.M. A<'<'. Cltnn. Rts. t9S9, 22. SS-61. tsci. H.; Ma.'\00,
W. R. ln<N'JI. Chtm. t985. 14. t761-t76S. FOf'dycc , W. A.; Brummer, J . G .; Cr011by, G. A.
J. Am. Cltnn. Sue. 1931, /OJ. 706t-7064.
722
1 S Organometallic Chemistry
where RX is a halogen, alkyl halide. or hydroeen. In other words oxidative addition

leads to the formation of a meta l-metal bond. Unlike the usual oxidative addition. ,,..,
mrtal r:enters are involved simullaneously. The reverse reaction. reductive elimination, may also occur.
(15.194}
RX
We can follow our suppositions regarding the formation of an M- M bond upon

oxidative addition by watching the change in bond length:
dl'l-1'1
(15.195)
= 292 pm
The greater the overlap of the metal d.;: orbitals. the greater the repulsion in the
reduced. JH state. and the stronger the metal-metal bond in the oxidized, J6 stale. We
should expect oxidative addition to be least favored at very long metal-metal distances, and much more strongly favored at those distances corresponding to the
normal metal-metal single bond distance, and this is what is found. Conver.;cly. the
longer distances favor the reverse, reductive elimination reaction. Indeed, with some
bimetallic complexes reversible addition/elimination of H1 can be accomplished, not
with molecular dihydrogen, but with a hydrogen donor molecule such as a secondary
alcohol:
(15.196}
Although the reaction in Eq. IS. I% is potentially catalytic. true
has
been achieved. However, when "M 1" il; [Pt:(pop).f-, solar-ilriven catalytic oxidation has been observed.:!UI In monometallic Pt(lll complexes the HOMO-LUMO
transition is in the UV region with perhaps a tail into the violet. The .:omplclcs un:
thus white or perhaps yellowish. The interaction present in bimetallic .:ompl.:xes. as
shown in Fig. IS.SO, narrows the HOMO-LUMO
such that this transition may be
shifted into the visible region. The electron may thus be excited by solar
(15.197}
..
The excited diplatinum complex is now predisposed to react further. The incipient
Pt-Pt bond is partially formed and addition of hydrogen is enhanced;:OO
[PtJ(pop)4]- + Me1 CHOH -
(H-P!Ux>p}.Pt- H]-
+ Me2C=O
(15.198)
""' Roundtou. o. M. ; . Atrt. a ,.. So<. ttaS. trn. 4lS4-4356.

,., Sweeney, R. I.; Ha<Vey. E. L.; Gray H. B. CO<Nd. CMm. Rtt. 1990. 105. 23-}4.
Stereochemicolly Nonrigid Molecules
723
Reductive elimination of dihydrogen may then take place to complete the catalytic
cycle:
(15.19\l)
In addition to conve rting secondary alcohols into ketones. the platinum caialyst also
converts toluene and other benzyl hydrocarbons into dimers.
Similarities between (Ru(bpy)))z .. (discussed in Chapter 13) and (1'11 {pop)4 )4 - are
apparent. Reactive excited states are produced in each when it is subjected to visible
light. The excited state ruthenium cation, (Ru(bpy>,JH. can catalytically convert
water to hydrogen and oxygen. The excited s tate pla tinum an ion. (1'1 1(pop).J.. -. can
catalytically convert secondary alcohols to hydrogen and ketones. An important
difference. however, is that the ruthenium excited state species results from the
transfer of an electron from the metal to a bpy ligand . while in the platinum excited
state s pecies the two u.-.>aired ele<:trons are metal centered. As a consequence.
platinum rea.:tions can occur by inner sphere mechanisms {an axial coonlination site is
available ), a mode of reaction not readily available to the IS-electron ruthenium
complex.20l
Stereo chemically
Nonrigid Molecules
Chemists are pcone to think in tenns of static molecular structures. This viewpoint is
initiated by st.i ck-and-bal models and reinforced by regular inspection of molecular
structures determined by
methods such as X-ray
In
fact many molecules arc stcn:ochcmicully nonrigid. If the rearrangement leads to
configurations which are chemically cquiv-.alent, we say that the molecule is fluxionOn the other hand . if the rearr.angemcnt gives rise to chemically
molecules. we simply say that isnmt>rlsm hllS occurred . Fluxional molecules differ
from other stereochemicully nonrigid molecules in possessing more than a single
configuration repcesenting an energy minimum. Scvcrul such minima may
present
and may be accessible with ordinary thermal energies. As a ve ry simple example.
consit1er symmetric and unsymmetric hydrogen bonds !Chapter Ill. If in the symmetric
HF! ion the lluoritle ions are considered relativdy immobile with respect to the much
lighter hydrogen, the motion of the Ia ue r can be considcretl. to a first a pproximation,
a vihr.uiun in a JX>tcmial well with an average position midway between the
OuoriJcs (fig. IS.51ul. In
unsymmctric hytlrogen hunlls possess twn potcn
tial wells in which the hydrogen can vibrate (fill. IS.S I b), occasionully being sufficiently cxcitet1 thermally to jump to the other weii )U" In such a system the hydrogen
woulll be found in one por.:ntiul well or another by rupid melhot1s such as diffraction.
"'-'Roundhill. D. M.: Gray. H. 8.: Che. C-M. AN". Clrrm. H t9S9. 2J. SS-6t .
""' Obviously a Slruc1ure is no1
inslnNiy wilh X-ray
technktucs. Rather lhe
struelure is imlllntoncoos in I he scn:oc tl'olllhe rime period over which I he dltTr.JCtcd wuve inlerncts
or the mole-cule is
short with tcSpcCI IO the rrett\k'ncy or atomic
wilh lhc
mooioxu.
:o This definition includes al
nonriai<J mclcculcs havir1c iolenlial c.ncrgy noinima
.....r coniplr:lljons at those minrm:& includlns molecule such as lhe pseuolo<ul:&lionul PF, nnd
FctCOt, tCboplcr 61.
""' F
s3c:. both poacrnoal well$ an shown 10 be lhc Sllmc dcrah. In sener:1l ror a
ol" 11'\Jiy fluxional
hydroam :wch as -o-H ... N this is noaa rue. All ollhe
S)'Siem .,.. cnct'JClic:llty equlvnlcN. however. :llld have cquivolent potential wells.
724
f -
----H - -- - - - F
o---H- ---- -::-----0
Posilioo
i'<Hotion
lbl
Fig. 15.51 Energy and poSilion of lhe hydrosen mom in (a) lhe symmelric Hfi system nnd
(b) an unsymmelric 0-H 0 s.ysJem. In (a} lhe average position of I he hydrogen mom is
mMiway belween 1he fluoride ions. In (b) lhe positional sl<eiCh on I he ldl
1he
averoge posi1ion of the hydrosen in lhe left polenlial well and the dolled sketch represenls
Jhe average posilion for the ocher po1en1ial well. The height of the energy lrrrier is
quulitalive and not mean! to represent any particular system.
If the banier between the two configurations is thermally accessible, the system is
fluxional.
In choosing a method for studying a particular molecular structure or dynamic
process. it is essential that the time scale of the method be appropriate for the lifetimes
of Ihe species involved (Table 15. 12). Diffraction methods have time scales of ro- 18 to
10-:!0 s. which is rapid compared to the frequency of molecular motions. Obviously
lhis time period rel3tes to a single interaction between the diffracted wave and the
molecule, and the actual experiment must take a considerably longer period of time for
colleclion of the data. The resulting structure is lhus a weigh1ed average of a ll the
molecular configurations present, and this is commonly encountered as llrermttl ellipsoids of motion (Chapter 3). Consider again the molecular fragment in rJg. IS.Sib. If
the higher vibrational levels were occupied, the hydrogen atom would appear to be
smeared over the entire vibrational amplitude. If only the lowest vibrational level is
occupied. the hydrogen will show up as a half atom at one minimum and a half atom at
the 01her.
like diffraction, spectroscopic methods using ultraviolet, visible, or infrared light
are generolly much faster than molecular vibrations or interconversions, and the
Toble15.12
Time sco!H for strvctwal
techniques
Approximate time scale (1)
Technique
10-20
10- 11
10- 18
10- s
Electron diffraction
Neu1ron diffraction
X-ray diffraction
Ultraviolet
ro-
Visible
Infrared-Raman
to-3 _ .
Eleclron spin resononcea
Jo- to Jo-
Nuclear magnetic resonancea
ro- to 10_.
Quadrupole resonancea
to 10-8
MOsstlauer (iron)
I .,.
ro-7
Molecular beam
l
Slop.llow kinetics
10-3 IO'roz
Experimental separation of isomers , > 10Z
t - .
w-
--1
.:.
Stereochemicolly Nonrigid Molecules
725
spectra reflect weighted averages of the species present (cf. lhe broad absorption
bands in the visible spec Ira of transition metal complexes. Chapler 11 ). Tile remaining
speclroscopic melhods are slower. and the rime period of the interaction may be
compared to Ihat of the lifetimes of individual mole.:ular configurations. The nature of
interconversions between configurations can be sludied by such techniques.
Nuclear magnetic resonance techniques have proved to be particularly valuable in
the sludy of fluxional molecules.!O? The most common experimental procedure involves analyzjng lhe changes in NMR line
lhal occur with variations in
temperature. 'llle simplest dynamic process is one involving two molecular configurations that have equal probability. If lhe interconversion process bel ween 1hem is slow
on the NMR lime scale. as might be the case ala low lemperature. two separate sels of
equal-intensity resonances. one for each configuration. will be observed in the
inim. If we can raise lhe temperature of the sample sufficiently so that lhe process
becomes rapid on Ihe NMR lime scale. the resull will be a single sel of spectral lines.
and they will appear a1 the midpoint of 1he lwo sets observed at lower temperature. At
this high-temperature limit. the molecule is undergoing changes so rapidly that NMR
cannol distinguish the two separale molecular configurations. only an averdge. As an
example of a system of this lype. consider
The crystal
structure of Ihe molecule shows 1wo monohapto and two pentahapto cyclopentadienyl
rings. At 62 c. the 1 1'1 NMR spectrum consists of a single line (fig. 15.521.
with a dynamic process lhat renders Ihe four ligands equivalenl. As the temper.uure is
lowered. the signal broadens and gradually splits into two lines which sharpen inlo
equol-imensily singlets at - ?:1 c. At this poinl. the process whi<:h inlerconvens
mono- and penlahapto ligands is occurring slowly enough thai both configumtions are
observable in lhe speclrum. However. even at this lemp.!r.llure. the monohapto rings
are involve<! in a dynamic process 1hat avemges 11k! signals for the 1hree types of ring
protons. Instead of separate resonances in a 1:2:2 rn1io. only a single fairly sharp line
is observed due to r.1pid migration of the met:tl from one sile to anolher within each
ring. When the temperature is decreased further. this process also is slowed so that 1he
peak for Ihe monohaplo ligands broadens ami then collapses. eventually reemerging in
the expected pattern for three nonequivalem ring protons at - !10 "C. Similar NMR
behavior
been observed for (C5 H,I.S.:- showing thai at 30 c a .r-r. exchange
occurs between lwo
one T} 1 ring. Separah: p.!aks in":!.: I r:uio for the two types
of
a.re observed :u - 30 "C. wilh individual rc:Solnanc.:s for the monohapto ring
protons becoming apparcm as the 1.:mper.uurc is o.JccreaS<.>d
Auxional processes involving acyclic uns:llur.th:d hydrocarbon ligands. such as
allyls and allenes. are also common. For the .,. complex formed between terramethylallene and 1e1racartonyliron (fig. 15.531. the proton magnetic resonance spectrum
below -60c shows three peaks in the ratio 1:1:2. representing lhe three cis hydrogen
atoms. three lrans hydrogen aloms. and six hydrogen aloms in a plane perpendicular
10 Ihe carbon-iron bond. Wilh an
in lemperature. the spectrum collapses loa
""Sarnk!rOm.J. I.>y,HJmit NMR Specwosmp,v: AC<ldcmie: New Yotk. 1982. Mann. B. E. In

Ol'llonom<wlfic ChrmiSify; Wilkin.on. G.: Slime. F. G. A.; Abet. E. W. &ls.: Pe<g;>mon:
Oxford. 1982: Vol. 3. Ch"''t<r 20. Orrell. K. G.; Sik. V. ..\n11. Rrp. NMR S(IC"<'troJet>py tW7. 19.
79-173. l.>yn<1111i<:
MuJinrtic
Eds.; Ac:Klemic: New York. 1975.
10M
209
Colton. F. A. In D)1JDmiC' Nurlrur MIRMiic

F. A . Eds.: Acodcmie: New Yeti<. 1975: Cl>aptcr
Jackman. L. M.: Couon. F. A .

Stlft'lr41Src,py: Jackman. L.
Cotton .
10.
llouaenrd. P.; Mancini. M.; Sayer. B. 0.; McGlinchey. M. J. lrwrg.
1985. U. 'JJ-9S.
726
15 Orgonarnetollic Chemistry
Fig. 15.52 Prolan NMR

(IJ'C,H,h(.,S
C,H,):Ti from - '1:1 10
+62 c. The separate
resonances observed at low
temperature for the two
types of Cp rings szadually
broaden and collapse,
giving a sin&le line at 62 c.
[From Cotton. F. A. In
.Dynamic
Resonanu Spectmscopy;
Jackman. L . M.. Couon.
F. A., Eds. ; Academic:
New York. 197.5; Chapter
10. Used with permission.)
spedr.l of
6l 'C
.coc
J6'C
32 'C
26'C
tO 'C
-rc
-!7'C
single resonance for the aveJ':I&e environment of the twelve hydrogens as the iron
migrates over the allenc '" system.
In organometallic clusters, ligands frequently appear to move over the surface
of the metal framework. The lriosmium complex,
CH1CH3), in Fig. IS.S4 provides an example in which the alkyne moves over the
u,C
\/
CH,
c
11-FctCOio
c
II
c
/
'
- . CH,
CH,
CH 1
H1 C
\/
c
II
Jk
C
/""'-CH,
CH,
Fig. 15.53 Migr:llion of

iron in letr:ICatbonylletramethylallenciror(O).
Stereoc:hemicolly Nonrivid Molecules
Fig. 15.54
727
or
ho:havior
In S tllllc l
terminal carbonyl aroups are exchunaifll In So.ae 2 the olkyne lisaiiCI moves about the:
triosmium surrace an<l "-' il <IO<.'$ <o. the
carbonyl shirts to remain 1ram to it . (From
Roscnbcrs- E.: Br.te:kcr-Novnk. J.: OcUen. R. W. : Aime. S .: Gobello . R.: Osetla, 0 . / .
Organnmrt. Chem.. 1919.365, lll.l-li!S. Reproduced with permission. I
face of the metal triangle at eleY111ed temperatures but remains fixed at low temper.llures.lto Variable temperature proton an\! carbon NMR studies show that the
alkyne movement is aeoompanied by exchange of the bridge and terminal carbonyl
In addition. axial an\! radiul carbonyl groups are undersoing exchange. T he
variable temperature prolon NMR spectra are "hownin fig. IS.SSu. At -6SC we see
a spectru m characteristic of two equivalent ABXJ spin systems (the AB spins are the
>10
E. : Brxku-Novnk. J.: Gellert, R. W.: Aime. S .: Ciobcllo, R.: Osdla, D. / .
mrt. Cfrrm. 1911t . J()j, 161-185.
OrR"""'
728
lSOrgonometollic Chemistry
1:11
Cbt
Fig. 15.55 Observed Ia) and simulated (b) variable temperature proaon NMR spectra of
1be spectrum at -65 c. characacrisaic of two
cquiv01l<nt AUX, sr in ystcms. is produced when lhc
of the
on ahe meaal
surf,ICc is slowed sufficienlly lhat il is fixed in one posiaion on lhe NMR time scale:. At
+ 82 OC the alkync molo:cule is moving
on the metal sunace giving an aver..gcd
spectrum in which all methylene protons arc equiwlenl. (From Rosenbera, E.; Brucker
Chtm. 1989,
Novak, J . ; Gcllen, R . W.; Aime, S.; Gobeuo. R.; Osclla, D. J.
J65, 163-185. Reproduced with permission.I
melhylene prOions. which are diaslereotopic and therefore nonequivalenl). As the

lemperature is increased, the mulliplet signals broaden and collapse into a single
qu3rtet as a result of the free movement of lhe alkyne. By simulating the observed
5pectra (fig. IS.S5b), it was possible to delermine rate constants and an energy of
activation (60.4 :!: 2 kJ mol- 1) for the process.
A different type of dynamic process involving a polynuclear metal system has
been itlentified in
which has a distorted cubane-like structure
with three Ru-Ru bonds in the crystalline state (Fig. IS. 56). By following its methyl
and ring prolon resonances over a temperalure range from + 70 to - 43 "C
(fig. IS.S71. the complex is shown to
a dynamic process involving the
metal-metal bonds. At lhe low-temperature limit, the spectrum contains fealures
predicted for the static structure: two lines of equal intensity for the methyl protons
.-=. -
72-i
Stereochemicolly Nontigicl
Ftg. 15.56 Structure of

IICH,C,H. )oRu.S.t:.
[From Houser. E. J.;
Amar:ISCI<cra. J.;
R:wchf&&, T. 8 .: WilSon.
S. R. J. Am. CMm . Soc.
1991, lfJ. 7440-7442.
Reproduced with
pc nnission.l
F1g. 15.57
7U "C
6.0
5.0
Pt>M
2.4
2.0
t.6
Variable
tempcr:uure SOO MHz

proton NMR
of
((Mcc,H.I.Ru.s.l" in the
CH, and C.H. reJions. The
$p<!clr:l provi.le evidtnce
for a mc:tal-mct..l bond
havona :on
activati<>n cncrsy ur
S! lcJ
(Fruno
H UUS..'I". E. J .;
J.: Rauch fuss. T. B-:
Wilson. S. R. }. AM .
1991. I IJ.
with permission.)
730
1 S O.VonOII>etollic Chemistry
r@Y
oc..
cO
Fig. 15.58 Eneray bamcrs tin kJ mo.-'> ror three sepanue types or rotational motion.
involving a brid&in& vinyl eatbyne lisand. The
were obtained by line sh:lpe analysis or
variable tempei'O\ture procon tiMR spedta. [From Ca$ey. C . P.: Konincs. M. S.: Marder.
S. R. : Takeuwa. Y. J.
1983. JJ8. 347- 361. Reproduced with permission.)
and eighl lines in the cyclopentadienyl region for the two ABCD sets of ring protons
(all ring protons are inequivalent due to lhe overall chirality of the complex). Coalescence to give a single methyl peak and two pe31cs for the ring protons occurs as lhe
temperature is raised 10 70 "C. a result that is a...cnOed to Ru- Ru bontl mobility. A
rearr.tngement pathway involvq a Dw intermediate has been
A final example of stereochemical nonrigidity, illustrating the applicalion of
sophiSiicalcd NMR line shape unulysis for oblaining rotational barriers. is providetl by
u cyclopentadienyl diiron complex containing a britlging vinylcarbyne I Fig. 15.511).!1!
Barriers for three distinct types of rotational motion involvina the britlging ligand have
been obtained: ( I) rotat.ion of the entire vinylcarbyne ligand (44.3 kJ mol- 1). (2) rota
tion of the dimethytamino group (45.6 kJ mol- 11. and 13) rotation of the aryl group
(54.3 kJ mol- 1).!12
Conclusion
Org.mometallic chemistrY. as name implies .

to both organic chemistrY and
inorsanic chemistrY. The tics to org:mic chemistry. :1t lirst in compounds that were
compllncnts uf
more ur less laboratorY curiosities. have bu')IClli1Ctl into
the petroleum chemicals industrY. Transicion mcml Ul)l:mumelllllic: chemistry is
largely an extension of the coortlination chemistry of strongly bontlcd ligands. but
cluster chemist rY anticipates the polyhedral chemistrY of boranes with extreme ..Je
localization in molecular orbitals (Chapter 16). The concept of isolobal fragments also
ties I he two disciplines together. with fragments as seemingly disparate as CH,C and
(0Cl 3 Co being isolobal. The entire 1\eld continues to expand as seen by the American
Chemical Society's decision to eslublish a new journal
in 1982 and
by the appearance of at least eight textbooks on organometallic chemi,;trY since then.
It will be especially inlerestina to observe the imp:JCt of organometallic chemislrY on
production or pharmaceuticals.
Md ceramic materials. as well as its
continued connection to organic feedstocks and energy production.
m Hous. E. J.; Amar:>sdc<n. J. ; RauchCIN. T. B.: WiiMln. S. R. J. Am. Clu,, $nt'. t,l . IIJ.
m C3$CY. C. P. ; Konin&s. M. S.; Morder. S. R.; Tal<--. Y. J.

347-:!61.
Chmr. t9A. JJ8,
Problems
Problems
731
15.1
A cyclopcntadien)ll phosphorus compound. (Me,C,)(Bti11PCI. lias been ideruified spec

troscopidlly.'" 15 this un organometallic CX!mpound? Explain your answer. By elrctron
countina. tlraw conclusions uboutthe hopd<:it y of the cyelopentadienyl &roup. How many
electrons does phosphorus need in order 10 obey the effective acomic number rule?
15.2
Ahhou&h U! valence electrons ore found in (

rule is violated. Explain.
15.3
H: OI..f+. t he effective atomic number
Formulate neutral. IS-electron complexes of chromium which cont:lin only
a. cyclopentodicnyl and nilrD$yl lipntls

b. cyclopenllldicn)ll. carbonyl, ond nitrosyl llsan.Js
15.4 Postulate ;eometries for bis-. Iris-. lind tetrakls(t riphenylphosph inelpollollium. Which of
these obey the llklectron rute! Whal is the aeometry of (Pdct.,l'-? Why Is it dilli:rcnt
from that o f the tetrakis(triphenylphOsphinel complex?
tS.5 Predia the metal-mttal bond order for neutral c,o mplexes lulvinQ the fonnula ltOCl.MCw
PR: l: N CCOIl when M V. Cr. :IIlii Mn.
t5.t. Complexes uf CS arc known. but homoleplic Coli lisands the samel examples such as
FeCCSI, lulve n01 been
Wlly do you think efforts ro prepare these cumplces
llave failed?
15.7 a. Complexes cont3ininQ l'ti2PCH 1 CH 1PPh1 sometimes known as d iphos. are abunclant.
Using the 1&-eleclron rule as auiclc. draw structures o r
i. IOChWtPf>h:CH, CH, PPh: l
ii. tOCl.WIPf>h:CH:CH: PI'tl: l

iii. lOCI.WCPPII,CH:CH, I'Ph:):
iv. tOCt.,W,cPPh,CH: CH:PI'h:l
v. IOCI.W,cPPh,CH:CH:Pfll,l:
h. It has not been po"l>iblc to synthcilc (0CI 1.,W:(PPh,CH , PPh 1l. but tOClouW:CPMc:C H1PMc:l is knuwn . Provide un
15.1! Postulate u monometallic
Mly 1hc Jigan\ls
complex chat ubeys chc
rule an\1 contains
a. hy.Jrllfl"n. acyl, cycluhuw.Jicne. an<l

h. thil>latc.
c.
1-cn?.cnc. an.J phoph oM

c:orl>ync . :on<l nilro.yl
\1. cydobcptalncn)l .
llll.l t:<l.:):tno.Jc
15.9 Trimctallic cumplcxe cuntaininc phophi\lo hri.Jccs ar c welt known ." Assume thai the
IIC-elec:lrun rule i< uhcyc<l 3nd rm.tubtc a ruct urc fur IMnCj.t. PH:ICCOI.b.
15 .1 0 Q;xneuf and cowllflccrs have rrcp;are\1 FclI' Ph:PCH-CIRISII'l' -SCOMcNI'I'h,MCOI
which obeys che 11!-<:le<:lron rule."' Confinn that it <Ices and draw its structure . What is
the uxidacion sCale of iron in chi
15.11 Buch Me,P and P(OMc), huve hn widely

towaro 0 : and H,O. Which o f the.e t wo
rNtcccptUf'"! Why?
ficands. Compare cheir reactivities

is gencrIIY consi<lcred to be the beuer
1
15.12 Prefixes ubound in Of'JroltlOfiiCWUic nllmcnclalurc. The cumpiA!x Fe, tCOIJj.t.>'1 l.
m Cuwlcy. A. H.: Mehrolrn. S. K. J. MI.
> Powc:U. J. ; Sawyer. J. F.; Sllirolian. M.
S.K. 1910. /OS. :!074-:!075.

1989,6, sn-SIO.
" ' Samb. A. : Oancrseman. 8.: Oixncvf. P. H .; Mcnlli. C. 0rll<'flt1lttrtol/ics 1981. 7. 26-lJ,
732
1SOrgonometollic Chemistry
(CH,C=CCH 1)J, for example. con1ains ,.,, rl. and .J... Draw the strucmre ofU>is complex
and e xplain 1he mennina d each of prefix.
IS.IJ Substilulion rellCiions of pelyooclear rnellll
wi1h lerti:lry phosphines often
in<luce the fotm:llion of bricl&i"ll carbonyls. Provide an explanalion.
15.14 Lipnd.s are described with a variety of adjec1ives, some not used in this ellapler. Using
olher sources, 1ry to determine wha1 is meant by
a. an ancillary ligand
b. an amphoteric ligand
c. a sterically noninnocen1 ligand
IS. IS Suggest reasonable syntheses for
a. Moi/-C.H,t!COh
c. h/-CJHstRe(COI,CtOMell'tl
b. (OCI.CoMn(COI$
e. 111'-CJHsl:!ReH
f.
d.
15.16 Which one of lhe followina complexes do you lhink you would mOSI likely be able lo
isolale: Wz<COI..,. !W:(C0110f -, (W,(CO),.j. (W:(COI..,r.
or (W:(CO),nr?
15. 17 The mechanism of CO replacement by Lin Mn:(C01 10 was controversial for a number of
years. Some believed 1ha1 subsliiUiion firsl occurred by homolysis of lhe Mn-Mn bond
while Olhe.-s inlerpreled their da1a in favor of CO dissocialion. Crossover experimenls
107
wilh Mn 1( 1:CO)"' and Mn:(uC0),0 106 and also wilh '"'Re!(COho und
Re,IC0lto" 7
suppon 1he second inlerprelation. Discuss lhis mechanislic problem and explain how I he
illo1opie experimenls rule out homolysis d lhe Mn- Mn bond.
15.18 O.:ICrmine the number and symmetry designations of 1he infrnred-uelive C-0 Slrelching
modes in lhe following derivalives of Mo(COI..

o. Mo(C01sPR 1
b. ds-MoiC0t..(PR 1h
c. IT<ms-Mo(C01.(PR1):
c.
15.19 Sulfur dioxide may funclion as a ligand by forming a metal-sulfur bond or u mellll-oxygen
bond. Draw lewi.s s1ruc1ures for these interactions. U is possible 10 dislinguish between
1he IWO modes of ligation wi1h S-0 Slrelching frequencies. Explain. (See Green. L. M.:
Meek. D. W. 0'1/0nometollics 1989. 8. 6.59-666: Wojcicki. A. Atlv.
Ch.-m.
1974. ll. .
15.20 h.knlify u rc:.l'cnl(s) lhlll wiU e1Tec1 each d dlC following lransform:tlion.:
FeW ---. Fe( CO), ---+ {Fe(COI.J'- ---. (McFc(COI.I- -
IMeC(0)Fe(C01,1PPh 1)J- -
McCtOIH
15.21 Transition metal hydrides panicipate in a varie1y of rcac1ions involving loss of hydrot:<n.
In some insiMces it may be losl as H- (hydride Jransfer). in others H. loss occurs tpro1on
Jr.msferl. and in yel o1hers hydrogen is losl as H"(hydrogen a1om lransfer). Complele lhe
following reactions and categorize each as one of lhe lhree 1ypes.
a.
. ._
.....-j"-......
C
Ph 0
p!
1 .....-co
Ph H
'
+ {Ph,CJ(A,FJ.
(See Kuchynka. 0 . J.; Kochi. J. K.
1939.8. 677-1)116.)
II& Coville. N.J.; SJolzenbera. A. M.; Mueuenies. E. L J. Am. Ch<m. S.Jt.. 1983./0J, 2499-2SOO.
ll1
A.M.; Muenenies. E. L J. Am.
Soc. 1983, /OJ. 822-827.
Problems
b. OsH.IPMe,Ph))
733
KH -
(See Huffman. J. C.; Green M . A.; Kaiser. S. L .; Cuulton, K .
G. J. Am. Ch<m. S11c.
1985. 1&7. 5111-5115.)
c. HW(C0hi17'.C.sH,I + PI>,CO(See Hoffman, N. W.; Brown, T . L.
C/rl!m. 1978. /7, 613-!>17.)
15.22 Explain why W(CO),(C(OMeJMe] is far mO<e sl:lble than WtCO),(CMe1).

15.23 When CpFelCO),(CF,I reacts with BF1 the prodtiCI is [CpFe!COh!CFz}![Bf4 }. but when
it reac1s with BCI1 , CpFe(CO),(C03) forms. Propose a mechanism for these reactions.
What is the driving force for each reaction? (See Crupi. A. M.: Shriver. 0. F. Or11um>mrtollics 1985, 4, 1830-1835.1
IS.:z4 lsolobal consKierntions >"Uggest that it shoold he pessible to replnce the CH fr:ljjlnents of
tetrahedrane, C.H,, with ML. fragments. What ML. fragments would you SUQ8est'? Draw
struciUres of the complexes.
15.25 What metal fragment .
might you suggest fO< creating L,,MaML.,. analo1ous 10
HO=CH?
15.26 The carbidoheplnrhenium carbonyl cluster, [Re 7CtCObJ'- . is analogous to C,H; and
forms a SCI of bicnpped octahedral complexes of formula!ion

Suggest some [ML,r fragments which should be capable of capping [Re,CtCOb l'-. tSee
Henly. T . J .; Shapley. J. R.: Rheingold . A. L.; Geib, S . J . OTI(unomttal/ics 1988. 7,
441-448.1
15.27 A typical C-P-C bond angle inn PMe! complex is 102". but the cone angle for this
ligand is given as
111r
in Table 15. 10. Explain.
15.28 lsoml!riZOUioo o f dsMotCOl4(PI'h,h 10 tmns-MoiCOI.(PPh,h proceeds by; d issociative

while isomerizntion of t'LrMo(COI4 (P8u,h prOCeeds by an intramolecular non
dissocialive process. How do you explain theSe resulls? (See Onrcnsbou11:. 0 . J. lnurt.
1'119. Ill. 14-17.1
15.29 Bond lengths and angles have been determined by .,as phase eleclron d iffruction for rwo
similar complexes. Fc!C0t.IC:H4 l and
Identify which sci of dala Cl or
II) belongs to each complex.
- '-
c-c
opmo
C-F<:
c,.ni
__
u_
1.1<\
IOK.9
!11.7
41.6'
IS.JO Nitric oxide loses an electron rather easily to form n nitrosonium cation yet tendency to
undergo reduction oflen cau.'ICS diiTicullies when it is used liS a reagent for synthesis of
nitrosyl carhonyl complexes. How can you rationalize the ease ofoxidntion of NO with i1s
of reduction?
"" Deeming. A. J. In Conoprtl>eiUfw

Chemi.<try; Wilkinson. G .: Stone. F. G. A.;
Abel. E. A.. Eds.; Pergamon: Oxford. 1982; Vol. 4. p )lSI!.
734
1 S Orgonometollic Chemish'y
IS.JI bocyanicles, RNC. and nitriles. RCN. are boih well-known Jisands. Complexes such as
CrtCNR) exist. but not complexes soch as CrtNCRJ.. Compare the bonding chanocleristicli of these two ligands and accounr for the rclarive stabilities of rhese rwo complexes.
JS.l2 Predict the product of the fcllowing reacrion:

!hlC,H, )Mo(COl:(CNnl-
+ 2Mel -
J5.JJ Nirriles arc almost invariably bound 10 metals through nilrogon and e xist in a linear
An exceplion 10 this is {l)'-C5H,J(PI'h,)lr('1'-NCC6 H.OI. Draw !he Struc
Jure fOI' !his complex. Does il obey !he 111-eleclron rule? (See Chetcuti, P. A.; Knobler.
C. B. ; Hawthorne. M. F. Orga1H1mmrllics 1988, 7, 6So-660.)
15.34 Thermodynamically, cisMo<COI:(PPh1CH1 CH,PI'h:h is more stable than trans-Mo
(C0J,(PPh,CH 1CH 1 PPh,):. but (transMo<C0),(PPh 2CH 2CH 2 PI'h2
is more stable than
[ds-Mo(CO),(PPh1 CH 2CH1 P1'111hJ... Provide an explanation for !he relative stubilities of
these isomers. (See Kuchynka. 0 . J.; Kochi. J . K. Orgonmnrwl/ic:s 1989. 8 , 6n-686. )
nr
JS.JS The conversion of fac-Mo(bpy)(COI,{PIOMeJ,) 10 /ac-MO{bpy)(COh(P(OMehFJ by action of BF,OEt, ;s thouahrJO take place by passina through an intermediate conraimna a
phosphenium ligand. Draw structures of the reactant. the intermediate. and the producl.
tSe.: Nnkazawa. H.; Ohta. M. ; Miyoshi. K. ; Yoneda. H. OrRonomrtofllc:s 1989. 8,
6.lt!-644.)
IS.J6 Metul-phosphine complexes are ubiquitOus in organomer:lllic chemislry. There ure ulso
metallmed phasphoranes (l.,M-PRJ. phosphides (l.,M-PR,). and phosphinidenes
tlnM -PRJ. Give specific examples of eueh.
t5.J7 When CO becomes coordinated to BH, its stretching frequl!ncy increases. but when CO
becumcs coonlil\:lled lo Ni(COl. its
frequency dccrcllses. Explain.
15..311 Ooes the CO stretchina frequency incre..., or decrease: when

o. L of lnM- CO becomes more electron withdruwing?
b. CO of L.M- CO becomes coordinated to a lewis ac.id. A, ro become LNM -CO- A?
15.39 Suppose you were direct ina a research student who came to you and stated that he or she!
lllld isclated a compound lhal was eilher (al or (bl:
./""-... l'h,
Mc .Si
PI
0
......
)N-Ir-PPh 2C H,
Mc ,Si
I
Ph:
(bt
(I)
What experiments (Oiher than X-rny analysis) might you suggest to clarify the siruation?
!See Fryzuk. M. 0 .; Joshi. K. Orr;onomrtollic:s 1989.8. 'n2-726.)
15.40 Using Fig. IS.J3, predict the number of unpaired electrons i n
o. !Cp,Ti)
b. (Cp,Crt
c. Cp,Cr
15.41 Organometallic chemistry seems especially prone tO the dcvelopme<ll of descriptive

words and phr.JSCS. Although much of this language is sometimes con$idtrcd j<lrgon und
not allowed 10 enler the formul tirernturc. it is common in oral usage. See if you can define
rhc followina terms:
b. supe.rsandwich
a. open-faced sandwich
e. club sandwich
d. ringwhiu.cr
e. molecular broad jump
r. piano :<1001 molecules
Proble ms
8 A..fr.une complex
735
h. lriple-decku saoowich
I. bulle.rfly cluster
IS.4Z The synthesis or o
homoleptic uranium complex, UR,, has finally been
achieved. 119 Why do you think R (CH(SiMez),r was chosen for Ibis synthesis?
15.43 The complexes of

15.38 are convnercially available. Starting wilh complexes which
contain only cart>onyl ligands, suggest syntheses fOf' lhe following:
o.. CpV(C0) 4
b. CpFe(COhl
c. CpNiNO
d. Cp,Mo,(CO),
15.44 The averQge bond dissociution eneray for ferr<.>eene ls tarae (302 kJ moC 1, Table 15.91 as
you might expect, but il is even Jaraer for vanadocene (369 kJ mol- 1) . Can you suggest
any reasons that vanacJocene is more reactive even thou!:lt it is more
15.45 The react;on of Fe(CO), with (Et.NIIOHI in melhonol ot -78 OC Gives a mixture of
(FeiCOl.ICO!Hll- and (FeiCO).(C02MeH-as shown by infrared spe<:uoscopy. When
UOH is used, however, the sole Jl(oduct is
Explain. (See Lee,
S. W. : Tucker. W. 0 .; Richmond, M. G. /norg.
1990.19. 3053- 3056.)
15.46 Predict the product of the following nucleophilic addirion:
+MtU-
IS.-17 Di.'!<:uss ahc difference between fonnulorins CrtC.H.J: as dibcnzenechromium Ia) and as
bisthoxahaptocycloocxatrienelchromium (bl:
@()
6
tat
(b)
Oo these represent different d>emical SI)Kies or merely seman1ic variations? Suuest

experimental methods thar mit;ht dishnsuish between (o) Wid lbl.
15.48 When one mole of ll'h 11'),Pt{C:H.) Is trc:ued with two moles of BF,. ethylene is quan
tllively released and Jhe BF3 is comptelely consumed. The pro.luct consists of a si,..le
IXlmpound. which is mooomeric in dichloromett>ane solu1ion. F"mulale lhe product and
describe the bontliftll in it. (See Fishwic:k. M .; Ni!th. H .;
W.: Wallbridse. M. G. H.
lnu,. CMm. 1976, /J, 490-492.)
'"'Van 0er Slllys. W. G. ; 8urTI$, C. J.:
A. P. 0'1"110tMt<lllk 1989. 8. 85S-8S7.
15.49 Upon encounlerif'4:

uror had occurred. Why1
ror the firs! lime, YO\! might suppose that a
IS.SO McUlls in low oxidation st:ues are usually strong ..Wudna 1181tnts. Give an uample o1 a
mcJal in D zero oxid:llion sWie actina as an oJtidizinR agmt.
15.SJ Consider the carbonylalion of cisCH 1Mn( ''CO)(COI. with unlabeled CO. Assuming that
melhyl migration occurs, predict the products and their ratios.
15.51 In Jhe hydrogenaJion of an alkene usina Wilkinson's calalyst, RhiPPh,hiRCH=CH:lCIIHKHI reac1s 10 give RhlPPh,hCKsolvenll and an alkane. In Jhis r eaclion rhodium is
reduced from + l 10 + I and on alkene is reduced 10 an Ill kane. Who! is oxidized?
15.53 Using d:IJD given in this book, calculate the Standard enlhalples of
"- C(s) + H1 0(8) -
Ol 2S
c for:
CO(g) + H,(g)
CO,(g) + H,(g)
b. H,O(g) + COW 15.54 In this chapter we have eJUIIIIined example$ ol polyniKiear metal carbonyl complees as
well us simple metal aut.onyl hydrides. Consider now the polynuclear catbonyt hydride
comple. H:Os11C0)11 Rtttionaliu lhe ronnula!ion of this species. Fr om your oppliCillion
o( !he Uklcctron rule. what Cll/1 you say aboulthe suuc:turc of !his molecule? How is it
1$.9? tSee Churchill
similar lo or different from lhe complex Os 1(C0) 11 shown in
M. R.; Wauo:rman , H. J . /norg. Cltcm. 1980, 19. 239t-2395.1
15.55 On page 643 !he followina stalement was made. somewhat casuully, in reference 10
H:FeiCOI.: "The 13rge difference in lhe two ionizalion constums provided the firs(
evidence thm the hydr08Cn llloms in 1he c:omplex were bolh bound 10 the
alom lond
hence 10 the iron aloml ... Present svppon for this line of lhinkini.
15.56 Why llo alkenes Wid aromlllics compose such a large frxt ion of the products from the
reaction of 111\!lhanol wilh ZSM5 CEq. IS. tH m
15.57 Sucges1
a r <action mechanism for the followi11: base-induced migr:uion:
15.5H When
wilh AIMc... a songlc noniontc rrO<JtiCI ell is
obt:linc.J which shows a carbonyl strelching frequency of 1721 em- c:omp-Jretl to
IK75 em - for the slortina malerial. The 1H NMR hytlri<Je chcmicul shift chaniCS from
-S.S') ppm to - 4.72 ppm in going from reac:tantlo prodocl. However. when CCpltCpiNb<H)(COt reae1s with AIEt, to eive a single neutral prodUCI till. lhc CO s[fetcbins
frequency "hanaes from 1863 em- Jo t900cm- and the 1H NMR hydride c:hemic:at s!Ofl
from - 5.48 ppm 10 - 10.2 ppm.
structures for products I and II anti
rntionalize their infrared and NMR dalll.(See McD:ldc, C.; Giblon. v. C .; Santarsiero,
8. D.; Bercaw, J . E. 0I'Jiunomrtoflin 1988. 7. t-7. 1
IS.S9 The solid SIIUC magic angle spinning "c NMR spec1rum of Fe(COI s hows a sin1<:
absorption al -26 "C but two signals (rdlllive intensity 2:31 al - tl8 "C. Provide an
explanation for lhese spectrul ob.o;ervotions. (See Hansun, B. E.: Whitmire. K. H. J. Am.
Chrm. S<1c:. 19'.1G, /12, 974-977.)
15.60 The first
metal complex hns been prepared, The synthesi.
was achieved by an imerCSJing sequence of re:sctions. Oiazumclhane convened II.S
Problems
737
cycloocladieoeldiiodopllllinum(l ll in1o
Treaunenl d lhis complex wilh silver 1rinuoroacetale led lo replacemenl of bolh iodine
31oms wi1h lriftuoroacclule. Melhunoly5is gove (I.Scyclooclndienelbi$1hydroxymelhyl)plruinum(ll). Re:.c1ion of 1his complex wilh dielhylnrodicarboxyluJe reStJhed in
loss of water and intrnmoleculllr cycl izution tu form an oxamelollacyclobutane complex of
pl:llinum fran which the diene was replaced by IWO lriphenylphosphine litands. Draw
Slructurcs of each of 1he complexes and
in lhls sequence. (See Hoover, J. F. :
Stryker. J. M. J . Am.
SO<. 19119, Ill. 6466-6468.1
JS.t'il The firs1 example of a four-cleclron donllr. side-on bridgin11 lhioc.nrbonyl. [HB(pzi,Jbeen rcpor1ed. Druw Ihe s1ruc1ure of Ihis complex.
(CO):W(I)1-CS)Mo(CO),(indenyl),
Why is lhe bridging CS group in Ihis complex enlied side-un ins lead of scmibridj;ing'! !See
Doyle , R. A.; Daniels. L. M.: Angelici . R. J.; Slone . F. 0 . A. J . Anr. 01t111. Soc. 1?8,,
Ill . 499S-4997.)
15.62 Amino alkcncs such us H1NCHzCHzCH 1CH - CH 1 nrc cnlalycically convcr1ed ro fivemembered heterocycles by
Oive the s1cps of the reaction sequence
and incorporaJe them in1o Tolll\lln callllytic cycle. Present arguments agains1 formation
of an Ul-alkenc bond. (See Ci"'J1C, M. R. : Maries. T . J. J. Am. Chem. Soc. 19119. Ill ,
rOS-4100.1
Chap
er
16
Inorganic Chains, Rings,
Cages, and Clusters
from topics discussed previously in Chapters 7 and IS it should be obvious that there
is no sharp distinction between inorganic and organic chemistry. Nowhere is the
borderline less dislincL than in the compounds of the nonmetals. Some. such as the
halides and oxides. are typical inorganic compounds. but others. such as compounds
of nonmetals with organic substituents. are usually called organic compounds. I The
situation is further complicated by the tendency of some nonmetals to resemble
carbon in certain properties. This chapter discusses the chemistry of nonmemls in
terms of one such property : their propensity to form chains, riflllS, and Cl!Jles. Most
metals show less tendency to form compounds of this type, ami the length of the
c hains and size of the rings thus formed are restricted. However. the ease with which
both metals and nonmetals and combinations of the two form clusters has only been
recognized in the last decade .and an explosive growth in this brnnch of chemistry is
underway.z
Chains
Catenation
If there is a single feature of carbon which makes

a unique hr.mch of
chemistry devoted to a single element) it is its propensity to form extensive
This phenomenon is not common in the remain<ler of th.: perit><lic table.
In this area the nomc11clruure of the cl>cmist is imprcci.e. to sny th< lrast. Thus it i <ommon to
distmauish between '"orpnophosphorus compounds ."" such as l'l'h1 and Me!PISIPIStMc!. and
"inorpnic: phosphorus compounds." such as PCI1 and No1P,O. While the lalla- undoubtedly
hdong 10 the province ofinorpnic: chemistry, a chemin interested in lh< f<JrmeO" is ns ap1 to h< on
orpnic: as an inorpnjc cbemist.
! There is 001 -arcement 011 wh:U c<lmpounds should be called du""" Some believe that the rcrm
should be resJricled to compounds whic:h hllve melal- melol bofld.< JCouon. F. A.: Wilkms.Jn. G.
AJtunaJ lnmllonit: Cftr-mlsuy, Sth ed.; Wiley: New York. 191!1!; p lOB). O!hers take o bro..Jcr
view thllt include$, fur example, !lorane (no tncJal mom. present) or polyoxomctal
tonly
lonsrnnge melal-melalllonding pO<Sible).
) Thi i a poor definition of Org<lnic chemilltry. or course. Even the imp""l orpnic: compound
involve cnrboo and hydfO&cn. and inorpnic: chemist cannot
out Jhllt 1hc tno.'t
lntcre!llifla pans of orpnic chemistry uSlllllly inwlve
grou,. conwining
OJtY&cn. nilr'O&cn. sulfur. etc.
738
Chains
739
although the congeners of carbon (especially silicon) and related nonmetals exhibi1 it
to a reduced extent. Despite the fact that there appears to be no thermodynamic
barrier to the formation of long-chain silanes.
their synthesis arxl characterization are formidable tasks. Although silicon-silicon bonds are weaker than
carbon-carbon bonds. the energy differences do not account for the observed stabili1y
differences. The explanation lies wilh the low-energy decomposition pathway available to silanes which is not available to alkanes.4 In addi1ion to I heir inherent kinetic
instability. silanes are difficult to h:mdle because they are very reac1ive. Their reactions with oxygen. as shown in Eq . 16.2. appear similar to the alkane reactions of
Eq. 16.1:
3n+ I
C.Hlo+z + - - Oz - - +
2
.
Jn + 1
S.H1.+ 1 + - - 02
2
+ (11 +
(16.1)
nSi0 1 + (n + I)H 1 0
(16.2)
In fact both reactions are thermodynamically favored to proceed to the right. The
importam difference. not apparent in 1he stoichiometric equations. is the
of
10 be kinetically inert in
1he reaclive
activation which causes 1he
silanes.s
Further complications with silanes arise from lack of conveniem symheses and
difficulties in sep:lration. Nevertheless. compounds from n
I 10 n = 8 have been
isolated. including both straight-chain and bnmched...:hain
We should
not judge silicon's tendency toc:llenale by looking at these hydrides. however. sin.::c a
much ditTcrcm result is obtained when suhstituents other 1han hydrogen are prcsent.7
Factors other than inhen:m Si-Si hond strength must he involved because i1 is
possible 10 isolate a l:uge number of polysilane polymers:K
---------
AI 41)1) "C. Si:H .Jccump>SC< to" lim r:,T Jh:tn C! fl . II appears Jh:lt hccuusc or Ihe tow-lying
UI"'-KC"upic:ll 4.t ,., ),f orbitals d( st. mi(:rncKtn u( a hydrosen alom wi1h
c:l an
Si- Si htx1tl is
JRin:t!- M. .-\ . In
Nins:s. Clwi'"" .mJ
( ;,1111() l:.'lllfC"IIIS: RMinsoW . .\ , L. . Ed.; F.lsc:vic:r: New
tm.a
11lC diiTcren<.: in ;octi,atioo cnctyy can h< qua!ilalivdy .Jc.cribcd ""'follow-: The re-..ction of Eq. 16.1
can he ini1ia1cd hy '\lriking a match white the rc:acli(lO u( Eq. lh.2 mely
:dEuwing ox)'Gcn to
conta<;lthc silane. It has been Slated that ooc oflh< prcrequisiles ror the ynth<sis ofhi!;hc:r <ilanes is
a large :unotiiU ,1( COUt;lgC .
E. In Silimn OtNrti<tr;r: Corey. J . Y.: Corey. E. R.: OuSflllf, P. P.. E.t.: WiiA:y: New
YurS<. "XII.
1 Tu quote Ruh<rt Wc:s1 ...... lthool'f\ th< myth 11\;,1 silicon is not capahk ut tcnsive cocmuion "ill
pcr>isls. very bq.'< cyclic polysilanes h;"'' ba:n synthesized as well
p.tysilanc puly"'"' with
mok:<:uL'tl wal'hts in th< hundrctb< or thousarlds." l'urr .\ppl. Clrrm. 19112. .f-1. 1041-JR$0.
Miller. R. 0 .: Michl . J. Chr"f. H. t'Jll'l. 11'1. DS'I-14lll .
Jdrnn: 7.iq;lcr.
J. M.: Fearon. F. W. G .. Eds.:
in Ch<misary
American Ch,Tnlcal Socic.ty: Washington. DC. 19'!0.
t...r_.,...,.
740
161norgonic Chains, Rings, Cages, ond Clusters
Mnny different organic R groups have been incorporated into these polymers and n
may be as large as 7S0.000." Low molecular weight polymers in which one of the R
groups is H have also been produced. ao 'llleir wide range of solubilities and eleclronic
properties (electron delocalization occurs along the Si chain) have slimulated much
commercial interest in recent limes wiah possible applications in the areas of thermal
precursors to silicon carbide. photoinitiators, pholoconductors, and microlithography. II Fluorinated and chlorinated long-chain compounds are known up to and
incluc.ling SithFJ.O and
It is worth mentioning thai bulky substituents may enhunce the slability of silanes relalive to alkanes. For example.
can be distilled
but
decomposes lo
and Br! at 200 c.
without decomposilion :u 26S
The chcmislry of germanes is similar lo lhat of silanes.tl Heavier congeners of
carbon. however. show severely restricted catenation properties. Distannane,
is known. although it is unsaable . Plumbane, PbH4 is of marginal slability itself. and
hence a large number of heavier analogues is noa expected. alahough lhe interesting
compound Pb!PbPh 3)4 has been synthesil.ed.
Some oaher nonmetals such as nitrogen, phosphorus, and sulfur form chains. but
aheir chemistry is less importanlthan that of the polymers of Group IV ( 14). Although
chain lengths for nitrogen up to eight atoms are known (most of which are extremely
and hydrawic acid, HN) are stable at room
explosive). only hydrazine,
temperature, :mc.l chains longer than 2-tetrazene, H2N- N=N- NH 1 , require
organic subslituents.ll1lle series of sulfanes, HS.H. is fairly extensive, and chains up
to " = I! have been obtained in pure form. Diphosphine. P! H, (very air7sensitive). is
well known. and triphosphine, H,PPHPH has been fully characteri7.ed. Tetmphosphine. H:PPHPHPH:. and higher"analogues have been idemified specaroscopically in
mixtures.t The open-chain structures become increasingly unstable relative to cyclic
strucaures Jof which there are many) as ahe number of phosphorus atoms in tbe chain
increuses:
c.
(16.3)
Oxygen forms no chains longer than three atoms, and besides the familiar owne, 0,.
and its anion. 0). few compounds are known; all of ahem are bis{perfluoroalky.l)
trioxic.les such as F)COOOCF).
1\llotropes of both sulfur anc.l selenium are known in which helical chains or greut
chains are unstable with respect to cyclic s. the
length are present. While the
chain form for selenium is most stable. Red phosphorus is polymeric anc.l is thought to
involve chains of pyramidal phosphorus aaoms.
v Weosx.. R.:
J. In lnm11"ni<' tJIId
P<>lymrrs; Zeldin. M.: Wynne. K. J. ;
Alkock. H. R.. Eds.; ACS Symposium Se.-ies 360: Amerian Chemical Society: Wnshinjllon. OC.
1988.
Wcot. R. J. Ors:wwmet. Clwm. !986, ]()(), l27- J46.
" The bond gap In polysiloncs Dppf08Ches 4 cV compared to nearly 8 eV in saturJtcd carhoo
<kelctom;. The poly<ilanC$ are insulator< in pore rorm but orten can he
to give ""mi
cnncluctorx.
o: As with Si. hiah molecular weight polymers- CR;,Oe).- hnve been rceendy char.><:terizcd. See
Footnote 11.
'' Bk. J.: Str!lhlc. J.
Chm. Int. EJ. EIIJI/. 1988, 17. 896-901 .
Baud!er. M. AnRf'W. CMtn. lnl. Ed. Engl. 1982.11.492-512.
Choins
741
1lle halogens are known 10 form reason:lbly stable chains in polyhalide anions.
the best-known example being the triiodic.le ion. 1) . Thty are considered separately in
Ompter 17. A great number of nunmetuls form simple X - X bonded molecules:
P:l
S:Cl:.
(hulogens), ere. In gener.tl these are
relatively stable. alrhough ull are susceptible to attuck by reagents that can clea ve the
X-X bond:
R1 AsAsR 2
0 2 BB01
0
+ X1
+ CH,=CH 1
2 + OH-
(16.41
2R 2 AsX
HCIO
HOOH
(16.5)
CI2 BCH,CH1 BCI,
+ CI-
(16.6)
(16..7)
H:O
H2 PPH: -
NH,lll
PH3 + (PHI.,
(16.8)
(16.9)''
cw!'
N: + 2H:O
The extensive chemistry of metal-metal bonds is sufficiently imcresting to warrant sepamte rn:at ment (page 807).
HeterocQtenotion
Although there is a paucity of inorganic compounds exhibiting true catenation, the

phenomenon of heterocatenarion. or chains built up of alternating :uorns of different
elements. is quite widespread. While hornoc::uena.ted polysilanes are nearing convnerhetcroc:uenated polymers
cializat ion (page 739). there are two classes of
that already enjoy wide appliC3tion . r These are the silicones. (R:SiOI.,. and the
polyphosphazenes.
... discussed on page$ 749 and nl. respectively.
The simplest heterocatenaled compounds are
formed by the dehydrarion of
acids o r their salts:
o-]
O=f - oH
2
[
o-
oo]
O = f - o - r =O
o-
+ H:O
(16.10)
o-
Such dehydr.tlions were first

by tho: uctiun of heat on the simple acid
phosphate salts and hence rhe resulting product w.1s termed pyrophosphate (Gr. 1TVfJ, fire). With an increased number of polyphosphates (P"03.,. cl'"+!o- known, however,
the preferred nomenclature has become diphosphare (n "' 2) , criphosphate (n
3),
etc .
For many heterocatenated compounds there are ot her, somerimes simpler, syn
thetic routes than the thermal elimination of water .
rlllhcr rhoon dca\'liJC u in rhc othcrc"""1'l wn be lllln'bulalto Jhe uorcmcty

otl(>lc bon.! in molccubt nilrOJ<fl.
utHl 0rJ:unontrlllllh' I'J/)11wrs: Zeldin. M., Wynne. K. J.: Allcock. H. R.. Ed.<.: ACS
SymplOium Selia 360, Aonc:ncun
Society: Wasl\in&Jon. DC. l\1118.
"'The
7 42
1 I> Inor ganic Chains, Rings, Coges, and Ctvslen
II
(16.11)
HO- S - 0- S-OH
II
II
0
'(16.12)
Condensed polyphosphates such as sodium triphosphate are of great indust rial imporsince they are used in large tonnnaes as ' 'builllers'' in the manufacture of
detergents . As such they function to adjust the pH and to complex water-hardening
ions such as
and Mr.n lndustrially, sodium triphosphate is not made from the
of sodium hydrogen phosphate and sodium
reaction of Eq . 16. 12 but from
dihydrogen phosphate mixtures:
(16.13)
Sil icate Mine ralsll
Silicon forms a very large number of compounds containing heterocatenated anions.

These are of great importance in the makeup of various minerals since about threefoonhs of the earth's crust is silicon and oxygen. Simple silicate anions, Si01-
....
/
/
,0\'; ' ',

l '
l
\
'
-A
'
(al
0=-----o/
1<1
(dl
Fig. 16.1 Various silicare sJruc:Wres: (a) SIO. lelr..lhedron. Wllcn carryina" -4 ct.arac.lhis
is lhc Dt1hositicale ion. (bl The disilic:ale anion. (c) Portion of an infinite sinGle chain.
(Sio ,,;--. (dl I'Qnion or an inflnilc dOilble ch:lin or bond. [514 0 11!'.:''. (el I'Qnion of a sheet
or layer
(Si,o,f;;-.
"Nicuwetllluiuo, M. S.; Peters. J. A.; Sinno:=. A.; Kleboom. A. P. G.: van Bckkum. H. J. A<n.
Clwm. S . lt35. t(l'l, 12-16.
111 t.iebau. F. Stmct11al Ctomtisuy ofSiliculu: Sprirccr-VCftllg: New Vorl<. 198S.
Chajns
743
(orthosilicates: Fig. 16. 1a). ure not common in minerals. al though they are presem in
olivine. (Mg.
an important constituen t of basalt which . in tum. is till! most
voluminous of the extrusive rocks formed from outpouring or maamu . Alt hough not
ocrurring in nature. both Na.Si04 and K4 Si04 have 11lso been shown to be orthosilic ates.t9 Other minerals containing discrete orthosilicate ions are phcnucito:
willemite
and 7jrcon (ZrS i0 4 ). The large class o r garnets is composed of
minerals of the general formula
where M11
be Ca2 . Mg!+. or
2
111
Fe . and M is At' - Cr J. or Fe'
Minerals containing the pyrosilicate or disilicate anion. Si.o;- tFtg. t6. 1bl. are
not common: thortveitite, Sc2 Si 2 0,. hcmimorphite, Zn4 (0HI;Si20,H 20 (does not
contrun discrete
ions). and bnrysilite. MnPb,.(Si20 7 1J. as well as vesuvianite
and epidote which contain both SiD!- und
ions . Linear tri uoo tetmsilic;ues
are almost unknown.
Although the t.e rm "discrete" is universally applied to the orthosilicate anion and
sometimes to the disiliC81e anion. they cannot be considered analogues or perchlor.ue.
ao;- The metal-oxygen bond in all silicates contains considerable covalent character
(just a.s the silicoiHlxytlien bond contains considerable ionic characterl. The orthosilicates contain no Si- 0-Si linkllges such as are present in the disilicate. chain
silicates. and the cyclic compounds. Although one can formulate them as
Na;tSiO.J4 - . Zr''(SiO.l - . or
as the more electropositive metal
(M"- Na. Mg!+, Fe!t. Zn 2, AI, .. ) becomes more like silicon in cbat:scter. it
becomes more
to discern discrete silicate <tnions. When M = Si. it becomes
impossiblo: and the result is Si02 (page 744). Thus lhe aluminosilic-.ues usually are
treated large covalent structures. and the hemimorphite
itbove is bener
viewetl as a 3-D structure rcl:llcd lo the aluminusilicntcs than as 4Zn: , 10H- .
H!O.
Alternatively. one can treat silicates as closest packed
of oxide ions with
Si4 + ions fitting imo
holes un<.l other metal ions lining into either
tet rdhedral
as in phenacite or octuhedr.ll holes us in olivine. tSee Fig. 7.3 for the
alternative ways of describing olivine.) Transition metal ions in these structures
bo!have Ihey do in
Olivine gets its name from the @reenish color caused
by
suhstitution of Fe! for Mtr+ ions in the octahedral holes. The hexa:tq uaimnllll ion
a simil:tr green color. The hue of ttarncts als" comes from
t mnsitiun lllctal
T he next higher order of complexity consists or the o-c;.llcd mctasilicatc unions.
which arc cyclic structures!Cl of gcnentl formula ISiO,,;. - occurring in beniloile,
BoTiSiJO,,. catapleitc. Na 2ZrSi,O.,H:O. dioplasc. Cu1,Si,.OtKf>H:O. and beryl,
Be,AI!Si,.Ot T his is the mosl important mineml source of heryllium. and also may
form gem-quality
tsce Problem 16.\1).
Infinite chains of formula (SiO)I;" - are found in
called pyroxenes. In
these chains the silicon atoms share two of the four lctrahcdro1lly coordinated oxygen
atoms with adjacent atoms !Fis. lf>. lc). Examples of pyroxenes include enstatite.
MgSiO,. diopside. CaMg(SiO,I:!. and 1he lithium ore. spodumene,
If
fun her sharing of oxygen aloms occurs by half of the s ilicon atoms. a double chain or
band Slructurc is formed. This is the structure found in amphiboles (Fig. 16. 1d).
Amphiboles cont:lln the Si4
repeating unit as well as metal and hydroxide ions. for
0
0ti
"' Barker. M. G.: CA>CXI. P. G. J . C/w.,. H-. . t9ftt. !N.

:The C)Ciic silie>tes ""' a>mitkred t.ter in the section nn inorpnic rinG
744
16 1norgon ic Chains, Rings, Coges, oncl Clutrs
example, aocidolire,
(also known us blue asbesros). and
amosile (Mg. Fe17(0H)1 (Si40 11 )z. a gray-brown asbestos.21
Further linkage by the complete sharing of three oxygen :1toms per silicon (analogous to lhe edge bonding between many amphibole bands) results in layer or sheer
struclures (fig. 16.1e). This yields an empirical formula of
By itself. il is a
r.uher unimportant structure. However. if we inlerwcuve layers of gibbsite. -yAI(OH)J or brucite.
we o btain importanl mineral structures: (I) A structure
of repeared silicon layers bonded to aluminum layers with bridging - 0 - and
-O(H)- is present in the kaolin (china clay) minerals.
(2) A structure of repeated pairs of silicon layers with aluminum layers between (and bridged
(3) If the AI in
with) - 0 - and -O(H)- is present in pyrophyllite.
is
the kaolin strucrure is replaced by Mg. the serpentine structure,
for med. The dimensions of brucire , Mg{OH)z. are slightly larger than those of the
Si 20 5 sheet. so the composite layers tend to curt Fibers from the curled layers form
chrysotile or white asbestos. (4) Similarly. talc. Mg)(0HhSi4 0 10 is the magnesium
analogue of pyrophyllire. These minerals rend to be relatively soft and slippery.
Further substitution can occur with one our of four silicon atoms in each Si4 0 10
unit replaced by aluminum. Because of the difference in charge between AIH and
s."', a +I c-.uion must also be added. This muscovite (white mica), KAI,(0HhSi3AI01n, is related to pyrophyllire. PhJQSOPite (Mg-mica), KMg3(0HhSi3AI0 10, and
biotite (black mica).I<(Mg.Fe)3(0H)1Si3Al0 10, are similarly related ro talc. The micas
are hard since the layers are composed of strong AI- 0-Si bonds. However, they
are relarively easily cleaved between the layers which are held together by lhe
electrostatic interactions with the potassium cations.
There are more complicated slrucrures inrermediare between pyrophyllile and talc
with variable substilution of A1 3+ and Mi+. Electroneulrality is maintained by
hydrated cations between layers. Thus the rnontmorilloniles are unusual clays forming
thixotropic aqueous suspensions that are used as well-drilling muds and in nondrip
paints. They are derived from the fonoolation AI2 (0HhSi4 0mxH2 0 with variable
amounts of water, Mi'+ (in place of some AIH). and compens3ting cations. M"+
tM = Ca in fuller's earth, which is converted to bentonite. M ,. Nal. Vermiculite
likewise has variable amounts of water and cations. II dehydrntes lo a laic-like
strucrure with much expansion when healed (see puge 750).
The ulrim;uc in cross-linking and sharing of oxygen atoms hy silkon
the
complete sharing of all four oxygen atoms per Si04 tetrahedron in a
structure. Silicon dioxide can exist in severul forms such as ljllart1. (thermodynamically stable at room temperature). tridymile. and crislobalitc. as well as
more dense varieties such as cocsire and s tishovire that form under high pressure.
With the exception of the Iauer. all of these contain silicate tetrahedra with complete
sharing but with different linking arrareements of the lctrahedra.11 Firolly. 'lilicon
is a commerdal 1enn "A>I;ell 10 a wriel y of mincr..ts which con be W01/cn in1o muJerials which arc heat 1111<1 fire rtsi..ant. The moSI convnon o<bcslos !9S'I. or lh:!l in u.c)is chrysolite.
h does no1 penis! in lilna 1iuue nod is much less dDI\J,'erou lhan crocidoliJe. wlrich is known 10
CIIUK ubcsJosis and mofiJIIOI'I
8. T.: 8i.a;non. J.: Com. M .:
A.;
Gee. J. 8 . L
1990, UT. 294-JOI .I
:t AsbcsiO!!
SiO: polymorph. hH
>ilic:on. AIJhnuJh C<U'-ooorcin:lle
block uf inofllllliC >ilic.lleS. lhcfc :lfl'c
numhcr uC c'UUI\fllc' uf
sitictJes wilh .U-aoonlin:>re silicon. Sec Wcedi.-.. T. l .: de Jont:. 8. H. W. S.; Veer-nan. W. S. :
Ailken. 8. G. Nuturr 1915. J/8, 132-1$1.
>: SlisboviJc. a hisf>-prcssurc

silicon is I he.,.,.,..,_
Chains
74S
dioxide also
a glass with tho: tetrahedra disonlered so that no
order exists.
We have seen that AI' may replace s;-4 so long as electroneutrality is rrwintained by compensating cations. Three
of aluminosilicme framework minemls
are of importance: the feldspars. zeolites. and ultramarines.
The feldspars. of general formula
are the most important rockforming minerals. comprising some two-thirds of igneous rocks. such as
which is a mixture of quartz. feldspars. and micas. Feldspars wcut.h cr to form clays:
-IK(AISipMJ + 4CO! + 6H: O -
4KHCO) +
+ t!SiO: c16.141
The 1.eolites are aluminosilicate framework minerals of general formula

They are characrerized by open structures that permit
exchange
cations and water molecules (Fig. 16.2). In the synthetic zeolites the
aperture and channel sizes may sometimes be controlled by a sort of template
synthesis-the zeolite is synthesized around a particular organoammonium cation.
This yields channels of the desired size. The zeolite framework thus behaves in some
ways like a clathrate cage about a guest molecule !Chapter 8). The
of
zeolites also involves several other factors such as the Al/Si ratio. the pH. the
temperature and pressure. and the presence or absence of seed crystals:!
of
Na._SiO) + AlCOHJ,
s;, ..,, ..,;,.,..,..
sodalite
(16. 15)
ZSM-5
(16.16)
(16.17)
In some instances auempts are mmle to

nmurally occurring zeolites.
Boggsile. shown on the cover ol' this hook and discussed in Chapter 1. is one \u.:h
example. Its low abundance in nature restricts studies which could demonstrate its
Both n:olur:l and synthetic zeolites (Table lt..l l lind wide :opplicatiun as lion
exchangers since the ions can migrate r;uher freely through the <JI)Cn structure. Some
cations will lit more snugly in the o:avitics 1han others. In addition. certain zeolites may
behave as molecular sieves if the water adsorbed in the cavities is completely removed. Various uncharged molecules such as CO:.
and organic compounds
be selectively adsorbed in the cavities depending upon their size. Again. the zeolite
framework behaves similarly to a clathrate cage except that the adsorbed molecules
must be c:lpahle of squeezing through the prefonned opening r.sther than having the
>l
Smilh. J. V.
1988.88. 149-182. Thumas. J. M.: C;utow. C. R. A.
/IH"II
1987. J5. t-Ill. The wore! uotile. mcanint b<lilina Slone. W.l.< fir.u u:<ed by lhc Swedish scM:nli<t.
A. F. CromtC<lt. in t756 uncr he observe1l1ha1 walcr was evolved from uilbi1e when il w:>< hctC<l
in :1 tlcmc:.
!-<
Barrcr. R. M. In Z.Wiilrs : Ort:U. 8 .: Hocevar. S .: Pejovnik. S . Eds.: Elscvi<:r: Amtcrllum. 19l!S:

pp t- 26. Varuant. E. F. Pu,. Siu
in Zeoli1rs: Wiley: New York. t<JCJO.
746
16 Inorganic Chains, Rings, Cages, and Cluters
Fig. 16.2 Stereoviews of: (al sodatite. Na,.AI,.Si,O,.!H:O Iring sizes are 4
pmll:
tbl ZSM-S. Na,AI3Si,30 192 16H,O (ring sizes are 4, S, 6. 7 , 8. 10 URO pml]: Ccl mordenile.
Na,.AI.Si.o010624H,O (ring sizes are 4. S. 6. 8. 12 (760 pmJI. See also Fig. 1.3.
represem oxygen bridges: intersections of lines show positions of the aluminum and silicon
:uoms. Noce increasing size of pore apenure (larsest diameter given in parentheses). [From
Meier. W. M.; Olson. 0. H. Atlas of Zn>lite Struc:tur,. Types, 2nd ed.; Buucrwonhs:
Landen. 1987. Reproduced wilh permission. I
cage formed about them. Molecules small enough to enter, yet large enough to lit with
reasonably large dipolar and London forces will be selectively adsorbed.
Zeolites may also behave as acidic catalysts. The acidity may be of the Bfl'nsled
type if hydrogen ions are exchanged for mobile cations (such as Na +) by washing with
acid. If the zeolite is heated, water may then be eliminated from the
sites
le.wing aluminum atoms coordinated lo only three oxygen atoms:
Chains
747
Tobie 16.1
Some natwol Grid synlhelic
zeolit..
Ring lizn
4. 6, 12
4, 8
4. 6. 8. 10
4, 6, 8
4, 6. 7. 8. 10
4, $, 6. 10. 12
4, 6
4 .s. 6, 8. 12
4, 6. 8
faujasiteb
natroliteb
slilbiteb
Linde K
s.
s.
ZSM-5<
boggsiteb
sodalite
mordeniteb
rflob
Smilh. J. V. Cht Rw. 1.988, 88, 149-181. Meier. W. M.: Olson, 0 . H. Alltu tJ] uulltt
Structu,. T;nHs. 2nd cd.: Buuerwonhs: lon<lo!,
tm.
NDlural: 5Ub!llilulion at ions ollen occurs in nmur41 zeohles.

r
S)'nlbctic.
Na
Na
o, /o,_/o, /o, /o,_/o, /o

Si
AI
Si
Si
AI
Si
cf 'o cf 'o cf "o cf "o cf "o cf
'o
(16.18)
n,e
These will acl us lewis ucitls.

calalyric sires occur ul high tlcnsiry ;mtl
uniform
in heir activiry (as
10 amorphous soli<.lsl
of lhe
nature of the zeolites.
Heterogeneous catalysis by aci<.lic 7.eolircs is one of the most intensely investigated topics of chemistry.:u The reacrion of ammonia wilh methanol to give rnelhy1amine can be calaly7.al by acidic 1.eoli1e rho !Table 16. 1);lb
MeOH + NH, """:""'
+ HlO
T1lumus. J. M. J. C/wm. SCK.

TrnM. 1991, SSJ..S(I). Rat>.>. J. A.: Gjtb. G. J .
lM-lt90. Jt. JIIS.
:00 Corbin. 0 . R. J. Mul. Cctul. 19119. 19. 271.
::.>
(16.19)
Hr.
748
16tnorganic Chains, Rings, Coges, and Clusters
Quite remarkably the reaction occurs without the formation of the more thermodynamically favored trimethylamine. Although some dimethylamine is produced in
the reaction. the channel size in which the reaction takes place favors the formation of
methylamine. The process. as of this writing, is about to be commercialized by Du
Pont.
We have seen previously shape-selective catalysis by ZSM-S in the conversion of
methanol to gasoline (Chapter IS).l7 Other commercial processes include the fonnation of ethytbenzene from benzene and ethylene and the
of p-xylene. The
efficient performance of ZSM-S catalyst has been auributed to its high acidity and to
the peculiar shape, arrangement, and dimensions of the channels. Most of the active
are within the channel so a branched chain molecule may not be able to diffuse in.
and therefore does not react, while a linear one may do so. Of course. once a reactant
is in the channel a cavity large enough to house the activated complex must exist or
product cannot form. Finally. the product must be able to diffuse out, and in some
instances product size and shape exclude this possibility. For example. in the methylation of toluene to form xylene:
(16.ZO)
The .. linear .. p-xylene can escape from the catalyst much more easily than the .. bent..
m-ora-xylene (sc:e Figs. 1.4 and t.S).!II The o- and m-xylenes are trdpped but not
Under the acidic conditions of the catalyst they continue to rearr.mge, and
whenever a p-xylene molecule is formed. it can pop out and leave the system.
Conversion is thus essentially complete. Catalytic zeolites have been compared to
enzymes because shape and size are crucial for the catalytic action of both.:!9
Zeolites also provide convenient framework sites for activating transition metal
ions for reJox catalysis. lwamotoJO has described a Cu(ll)/Cutl) exchanged 7.colite
that holds promise for the high-temperature conversion of NO_. (in diesel and auto
cxhausll to
and
2NO
N! + 0:!
(16.21)
Reducing
city is enhanced by hydrocarbons (unbumt fuell which provide a source
of hydrogen.
Tmnsition metal ions in zeolites behave much as expected for ions in a weak oxide
field. but often the metal ions are found in trigonal sites. so their spectra and magnetic
properties are somewhat different from those of the more common octahedral and
tetrahedrallields.ll
"'Hilhlc:ric:h. W.:
M.; NaOmunn. F. Am:<'W. Owm. /111. EJ. Errxl. 191111.17. :r.!l>-246.
l1l Olit$U)I, S. M. C/wm. Br. 1985.11. 413-ln. Nllj)y. J. IJ.; DerWllllC. E. 0 .: RC!<ing. H. A.; Miller.
0 . R . J. Pify.. Cltenr. 198.l.IJ7. 833-H37.
l'l
Thoma.'. J . M. AIIJ.''""' Chm. /111. EJ. Etutl. 191111. 17. 11>73-1691.
Cl'"'"
M. : Yahiro. H.: T11nd:r. K.: Mizuno. N.: Mine. Y. : l<.;tjjnwa. S. J. Phy.f.

t99t. liJ.
37Z7- J73Q. S..to. S.; Yu-u . Y. : Yahiro. H .: Mizuno. N.: tw:.mo10. M. Appl. Cuurl. t991. 71J. LI-LS.
" Klier. K. WIIJ.'mUir 19118. 4. 13-25.

.:.
Chains
749
Another class of framework aluminosilicates is the ultmmarines. T hey are characterized by an open framework ami intense colors. They lliffer from the previous
examples by having "'free nnions unll no water in the cavities. UllnliTillrine blue.
which is the synthetic equivalent of the minerul lopis lazuli, contains radical anions.
S) and 51. The dominant S) gives rise to its blue color. Ultmmarine green also
contains these two anions but in comparable amounts. Although these two anions are
also found in ultramarine violet unll pink. the characteristic color is due to a third
species. perhaps S4 or S.l
Structur:tll y reluted. but colorless. minemls such as
sodalite (containing chloride anionsl and noselite (containing sulfate
are sometimes included in the broad cutq,>Ory of ultramarines.
The stl.llly of silicaceous minerals is importllnt, not only with respect to better
understanding of the conditions of fonnation and their relation to the geochemistry of
the.\e minemls. but also with respect to structural principles nnd the synthesis of new
structures not found in nature (synthetic :z.eolites and ultramarines))l
In all of the silicates discussed above. the sharing of oxygen atoms between
tetrahedra is by nn apex only:
o,
,0
Si-0-Si
o,l
0
\'o
0
No cases are known in which ell(:es o r faces are share.!:
0-Si
,o,
Si-0
\ 0......-..0
'-"'!
P..1uling has listed a set of rules for predicting stability in complex crystals based on an
ionic model.l" Although no one now accepts a purely electrostatic model for silicates
and similar compounds, Pauling, rules are still reasonably accumte as long as the
pm1ial charges on the atoms are sullicicncly larsc to make electrostatic repulsions
signilicanc. Such repulsions militme against the sharins of
or faces by h:trahco.lra
since this places
centers too
c:1ch uthcr.
No section on hctcroo::atcmu ion woulll be cumplctc wilhllllt a lliscussiun of silicones,
The term silicune
coincll by anulogy to ketone uno.ler the
mistaken belief that monomeric R..Si- 0 compounds coulo.l be isolated . Siliccn compounds that are formally
to carbon compounlls are found to have quite
clifferent
Thus carbon d ioxi<le is a gaseous monomer. bul silicon dioxide is
an infinite singly bonded polymer. In a similar manner. grm-diols are unstable relative
to ketones:
(16.22)
Clutk. R. J. H.; Di""s. T. J.; KUfTIIW. 111 . ltl<lt't. Cltttn. t911J.11. 2766-Z7n.
n For a roou
discussion uf sdialle millct:>l!>. - Wells. A. F. Stnt<tlll"ulln<>'!l"nC" Cltrm-
.ll
isJr]. 5lh eel.:
"For
Oxfo<: Lundon.,..., a...pter n.
.J;,cuosion....,
Uhaca. l%0; llP S44-56l.
lJ Rocllow. E. C. Sili'' "' und
L Tit<' Nuturt 11/tlt<' Cl,.mkvlllmrJ.xd eel. ; Cornett

Sprillca-Vet1ae: New York. 1981.
750
161 norgonic Chains, Rings, Cages, one! Ousters
The analogous silicon compounds are also unswble, but the "dimethylsilicone" that
forms is n mixture of linear polymers (and cyclic products to be discussed in the next
section):
Me
Me
Me
I
I
-0-St-0-Si-O-Si-0J
I
I
Me
Me
(16.23)
Me
Hundreds of thousands of tons of pure Si are produced eve.ry year by the reduction of Si01 in an electric furnace;
Si01 + C - Si+C01
(16.24)
Allhough some of this is used for the production of ultra-pure silicon for semiconductors and for alloys with iron. aluminum. and magnesium.
for the production
of methyl silicon chlorides:
JCH,O + Si 2CHJCI + Si
--+
CHJSiCIJ + C1 H,.
(16.25)
(16.26)
These products are separated by distillation and used to make over SOO million kg per
year of silicone rubbers. oils. and resins. All of these materials repel water and are
electrical insulators. The rubbers are flexible and the oils are liquids over a wide range
of temperarures.
Intercalation
Chemistry36
Intercalation compounds consist of layers ("sandwiches'') of different chemical species. The name comes from that describing the insertion of extra <.lays
as
February 29th) into the calendar to make it match the solar year. Most work on
intercalation compounds has been on synthetic systems in which atoms. ions. or
molecules have been inserted between layers of the host material . However. some
aluminosilicates that we have encountered above provide useful
Thus talc
and micas form layered structures with ions between the
sheets (Fig. 16.31.
Some minerals. including llll clays. have water molecules intcrcalcatcd t>ctwccn
framework sheets. In some. such as vermiculite,
water may
and tlr:m;uleave
than they
<.lilfuse
ically be evacuated by heating. The wuter
along the
occurs. The result the familiar exp..nded vermkulitc
used as a packing material and as a polling soil conditioner.
Another example of this type of intercalation compound is sotlium b.:ta alumina
where the sodium ions are free to move between the spinel layers. The sodium ions
can be replaced by almost any+ I cation such as: Li. K+. Rb. cs. NH;. HJOY.
n. Ga+. No, etc. The conductivity of these materials varies with the si7.e of the
ions moving between the fixed-distance (AI-0-AIJ layers.
Graphite is perhaps the simplest layered structure. The intralayer C-C distance
( 142 pm) is twioe the covalent radius of aromatic carbon (cf. 139 pm in benzene) an<.!
the interlayer C-C distance is 33S prn. twice the van tier Waals
of carbon. The
sheets are held together by weak van dcr Waals forces. Many substances
be
"'Whilliogham, M. S.; Dines, M. 8 .

Prc>fl. Clu-m. 1980, II. 5s-87. Bcnscnhard, J. 0 .; FriiZ.
H. P. AnRtw. Chtm. /111. EJ. EnN/. t98J. 11. 950-915.
Chains
751
(bl
bl
Fig. 16.3 layered silic:ue s1ruc1urcs: 131 talc.

(bl mu,;covile Ia mical
KA1,(0Hb!Si,AI0 101. (N<>t<': Ill Ele<:aroneulrnlily is main1:1ined by
of Kill.
Al(llll. und SillY). C2l Tile repe.uinglayers in muscovile are bound 1oge1her by I he K
colions.JJFrom Adams. 0 . M.
Solids: Wiley: New York. 1974. Re.pro<luced wilh
intercalated between the layers of graphite. but one of the longesl known and best
is potassium. which Ciln be imcrcalated umil a limiting formula of <;K is
This is known as lhefirst-staK<' cvmpmmJ. The earlier.lower stages have 1he
formula of C 11,.K. The stages fonn stepwise as new layers of potassium are
;tdded. giving wcllchardCicri7.ed compounds with 11 = 4. 3. 2. (fig. 16.4). The final
step (yielding
II includes tilling in :Ill of the remaining available si1es !Fig. 16.SI in
itddition 10 forming the maximum numb.:r of
Presumably. fun her intercal:ltion
c:nnol lake pl;cc
of clcctroslitlic repulsion.
Upon imcrc:llmiun. the gmphilc layers move apart somewhat
pml. 1hough
less than cxpe.:h:d as
frum
diameter of the potassium ion (304 pm or
greuter). This indicates that the K ion nests.. within the hexagonal carbon net. and
one can even
about weak complexing to 1he carbon ...electron cloud.
Fig. 16.4 S1aging in

grophi1e inlcrcalation
compound. C1:.,K.
Sc-..
Addilion of po!as..;um
ptocecds 1hrough n 4. J.
2 . . . 10 lhe timil in Singe
1: C1:..K-+ C.K . (From
Whiningham. M. S.; Dines.
M. 8. Surv. PrtiJI. Chtm.
1980. 9. SS. Reproduced
wilh pcrmission.J
752
16 lne><gonic Chains, Rings, Cogeo, ond Clusters
Fig. 16.5 Filling of

available hexagonul si1es in
layer of grilphi1e; For
1he limit of c.K. K e +
0; for C 1::.K. K
0 only.
[From Whiuingham. M. S .:
Dines. M. B. Sun. Prng.
1980. 9, SS.
Reproduced with
permi.ssion.J
The menlion of I he K + ion presupposes knowledge of the nature of the polassium

species present . Because of the similarity in energies of the valence ami conduction
bands. grnphite can be either an electron donor or acceptor. Intercalation of potassium
atoms into graphite resulls in the formation of K + ions and free electrons in the
conduction band. Graphite will react with an electron acceptor such as bromine to
form CMBr in which electrons have transferred from the valence band of the graphite to
the bromine. Appnrenlly. simple bromide ions are not formed, but polybromide chains
form inste<k! (see Chapter 17 for similar polyhalide chains). The expected Br-Br
distnnce in such a po[yhalide)7 (2S4 pml compares well with the d istance between
centers of adjacent hexagons in graphite (256 pm). In contrast, the expected CI- CI
(:!:!4 pml and 1- 1 (292 pm) distances do not til well with the graphite structure, ami in
In contrast. iodine monofact these two halogens do not intercalate into
chloride h:xpected average 1-CI distance = 2SS prn) does.
Both of the potassium and polybromide intercalation compounds are good con
ductol'l of electricity. In the potassium intercalant. the electrons in the conduction
band can carry the current directly. as in a metal. In the compounds of graphite with
polybromide. holes in the valence band conduct by the mechanism discussed previ
ously fnr semiconductors (Olapter 7).
Recently. it has proved possible to intercalate a variety of organic molecules imo
metal d ichalcogenides.ll< Unlike the above examples these do not usually
involve electron transfer. When single molecular layers of MoS suspended in water.
are sh;oken with water-immiscible organic molecules such as
the latter is
film results
adsori:led 11nto the former. A highly oriented. conducting
when exposed to a glass substrate. The interlayer spacing of MoS 1 increases by .560
pm upon ferrocene inclusion. II has been suggested thatlhe best chance for producing
a useful high-temperature superconductor may lie with incorporating an organic
superconduc1or into a layered inorganic compound .
One-Dimensional
Conductors
There is an unusual hetero chain, (SN).,, discovered in 1910, which d id not receive
detailed altention until the 1970s. Interest centers on the fact that althouGh it is
composed of atoms of two nonmetals, polymeric sulfur nitride (also called polythiazyl)
has some physical properties of a melaf. The preparation is from telrll$ulfur
tetranitride (see page 776):
(16.27)
S.:e Wells. Foolnote 33.
lll
Oivigolpitiyo. W. M. R.: Frin.ll. R. F.: Morrison. S. R.
1939. 146. 369-)71.
Choins
753
c.
1lle
is pumped in a v-.scuum line over
wool at ::!:!0
where it polymerizes
slowly to a lustrous golden
The resulting prcxluct is analyticnlly pure. as is
necessary for it to show metnllic propenies to u significant degree: it has a conduclivity near that of mercury at room tempenuure. and it becomes a superconductor at
low temperatures (below
Kl.
X-ray diffraction studies show that the SN chains have the structure shown in Fig.
16.6 . This chain can be generuted from adjacent squa re piHnar
molecules. The
S- N bonds in this st:u1ing m3tt:rial have a bond order of I .S a nd a bond length of
165.4 pm. intermedi:lte between single ( 174 pml and double (I S4 pml sulfur-nitrogen
bonds. A free radical mechanism has been
leading to 1he linear chains of
the polymer (Fig. 16.71. Since polymerization c;m take place wilh almost no movement of the atoms. the starting ma teria l and product are pseudomorphs and the
crystallinity of the fonner is maintained ..ot
If one auempts to drnw a unique Lewis structure for the (SNJ.r chain. one is
immediately frustr-.uet.l by the odd number of electrons available. Many resonance
structures can be drown and they contribute to the hybrid structure. but the single
structure:
:S= N: :S=N:
Fig. 16.6 ISNI, chains in one layer o( polymaic sulfur nitride . (From MacDiarmid. A. G.:
Mikulski . C. M.: S=ln. M. S.: Russo. P. J.; Cohen. M. J.: Bright. A. A.; Garito. A. F.:
He-.cr. A. J. In Compmmd.< ith Unusuo/ Prti{)Utlrs: KiOQ. R. B., Ed.:
in
Ch:mistry Series ISO. American Chemicul Sociely: WashinGton. DC. 1971'>. Re.,ruduccd wioh
permission.(
>"l.abe.<. M. M.: Lowe. 1'.; Nichols. L. F. CllrM.

t97f. 79, l-IS .
.. Mibbki. C. M. : Rus.\0. P. J.: S;onn. M. S.: M:ocOi:lrmld. A. G.: Gurioo. A. F.: Hcqcr. A. J . J .
Am.
a ...,.. S<K. t975. Vl. flllll.f>l6l.
This is in CDnlMI$1tO the more commonly observed re.ull o( sciill AJ;oJc

turning iruo an amorphoUs powder.
rc-..o<:Jions: bc:wlirul
754
161norvonic Choins, Rings, Coges, and Clusters
ti-S
N -- S
1!11
ILJI
S -N
S -N
N-S
I[J I
S -N
Fig. 16.7
ol
S:N, to rorm (SN), chains
wilh minimal movemenl or
uloms.
H- S
1[]1
S -N
N-S
I! \\
IS
11-11
N-S
_II
N- S
101
N===s
:s
N -- S
N-S
\\ __ II-II
N- S
No
illustrales many features: :1 conjugated single-bond-double-bond resonance system

with nine eleclrons on each sulfur atom rather than a Lewis ocret; every S-N unit
will thus have one antibonding.,.. electron. The half-filled, overlapping 'IT ortJitals will
combine to form a half-filled conduction band in much the same way as we have seen
half-filled 2s orbitals on a mole of lithium atoms form a conduction band (see Olapter
7). Note, however, that this conduction band will lie only along the direction of the
(SNI,. fibers; the polymer is thus a one-dimensional metal .""
Similor to (SN).. in their one-<limenslun31 conc.Juctivity properties are the stacked
columnar complexes typified by (Pt(CNI,I:- . These square planar ions adopt a closely
parallel arrangement. allowing ror cunsi!lerable interaction among the d .!
of the platinum atoms. These orbitals are normally filled with electrons. so in
order 10 get a conduction band some oxidation (removal of electrons) must take place.
This may be readily accomplished by adding a lillie elementa l chlorine or bromine to
the pure tetracyanoplalinate salt to get stOIChiometries such as K:[Pt(CN I.)Br0_3 in
which the plati num has an average oxidation state of + 2.3. The oxidation may also be
accomplished electrolytically. as in the preparation of Rb:[Pt(CNl 4 kFHFloA lrJg.
16.8), which has a short Pt-Pt separation. The Pt- Pt distance is only 280 pm.
almost as short as that found in platinum metal itself(2n pm) and in oxidized platinum
"pop" complexes (270 to 278 pm; see Chapter IS).<l Gold-bronze materials of this
type were discovered as early as 1842. thou11h they have been litlle uooerslood until
recent times. The complexes behave not only as one-dimensionol con!luctors, but
c Roundhill. 0. M.: Groy. H. B.: CIIc:. CM. M r. Chtm. Rrs. t989. 22.ll-6L Schull%. A. J.: Colrey.
C. C.: Lee.. G. C.; Williams. J. M. lltOrif. Cl>mt. 19'77. 16. 1129-2131 .
Chains
755
Fi9- 16.8 Perspective view or the unit cell .X Rb,(PIICNL.IIFHFI,, ..,.
cbllins
(PIICNI,J'- ions occupy the comen1 und center or the unit
The triad of
circles repr-nts the
occupi.:<l p..>Sitions or the FH F- ions.
the very
shan 1'1-1'1
1119.3 rmt. IFrom Schultz. r\ . J.: Coffey . C. C.: Lee. G. C.: Williams.
J. M . ltrtJr1:. Ch""' 1m.
Reprl>\luce<l ,.iJh permi"ion. l
or
!heir eleclrical pi"'(>ertics arc

roore complex . Oelaile<.l <.liscussion of the
many interesting aspls of
malet+.. ls is beyun<.l lhe scope of lhis book. bul
fonuootely there :ue thorough reviews of the
lsopoly Anions
Trunsi1ion metal> in !heir high.:r

s lates .1re formally similar lo nonmetals
wilh corresponding group numbcr1: V (VIJI and PI VA) in
a nd PO!- . Cr lVI B)
an<.! S (V IAl in
and
Mn CVIIBI and 0 !VIlA I in MnOi and CI04' . The
analogy may be exlendeo.l to polyanions.
as dichromate , Cr:O;- : however. the
differences in behavior bel ween the metal ;md nonmet3l anions are often more importanl 1han lheir similarilies. Whereas pnlyphosphoric :lCids and polysulruric acids form
only un<.ler r.1lhcr
dehydrating condi1ions. polymeriza1ion of some melal
anions occurs spoman.:ously upon acidification. Fur example. lhc c.h romale ion is
stable only at high r>H>. 1\s lhc pH is lowcrcll, pro1onaliun
..timcri7.atiun occur:
CrO:i- + H ' ___. tHOICrO ,-
(16.211)
IHOJCrOi + H. -.... lHO):CrO:
(16.29)
___.
+ H:O + ::!W'
(16.30)
Treatment wilh concentrated sulfuric acid compleles the dehydration process and red
chromium( VI) oxille ("chromic acid"l rrecipi1u1es:
II
, _
+ nH -
11lc slructure of Cr03
II
(16.31)
!CrO,)., + 2 H:O
of infinit.: !incur chain.' of
lc1r.1hedra.
t:nf'lkkJ l.PirtW' ('huins. Miller. J S . EAI. : l'knum: New Ylllt. 191C. Vol'- 1-11: Ill&), Vd. Ill.
then. J. A.:
L. J.: Madon>Cn. J .. Hnll'm:on. II. M. Srwn &IHJ111: tBulml 1981. JO, l-SS.
G1iemam. G.: y,..,;n, H. Sr,.,..t. 11uroJin1t cBrrlinl 1985. 61. 87-U).
7S6
16 Ino rganic Chains, Rings, Cages, and Clusters
Fig. 16.9 Dominant

oxoonklns of vanutlium
pre$ent in aqueous solution
as a function ot concenpH. (From
tration
Pope. M. T. Httrmpoly
unJ lsopoly
New
wi1h permission.!
> 3
vor
10
pH
Other metals such as vanadium have more complicated chemistry. The vanadate
ion. vo!-. exists in extremely basic solution (F.g. 16.9). Under
dilute conditions
as the pH is lowc:red. protonation occurs to Give monomers:
vo:-
vo30H1 -
V0 1(0H)i
VO(OHh('?) -
vo;
(16.32)
When solutions ate more concentrated. however. protonation and dehydr.ttion occur
to form [V
and higher vanadates. 44 Further polymerization occurs until hydrous
V!05 precipitates at low pH. The precipitation of vanadium(V) oxide from aqueous
solution as well as the simila r behavior of 01her metal oxides. such as MoO, and W03
stands in sharp contrast to the extremely hysroscopic behavior of the analogous
nonmetal compounds P20 5 and S0 3
The polymerization of vanadate. molybdate. and tU118Stute
forming isopoly
anions has received a great de31 of attention. Earty in the conclensation process the
cooruinution number of the metals changes from 4 to 6. anc.l thc basic buihling unit in
the
process becomes an octnhcdron of
oxygen atoms surrounding
each metal a1om. Unlike tetrahedra. which can only li nk by Nharing an apex. the
resulting octahedra may link by sharing either an apex or edge I rarely n face) due to
the relaxation of electrostatic repulsions in the larger octahedra. As a result. the
structures tend to be small clusters octahedra in the discrete polyanions. culminating in infinite structures in the oxides. When the edse sharing
place. the
structure may be stabilized (relalive to electrostatic repulsions) if some distortion
occurs such that the metal ions move away from each other. As the polymerization
increases. it becomes more and more difficultlo have all metal ions capable of moving
to assist in this reduction in electroslalic repulsion. Ultimately the sharing of edges
ceases since the requisite distortion becomes impossible. II might be expected that the
smaller the metal ion. the less the repulsion and the larger the number of edge-sharins
octahedra per unit. This expectation is borne out in u general way. For example. the
metal radii (Table 4.4) are vH (68 prn). Mo.,... (73 prn). W,. 174 pml. NbS+ (78 pml
or
... Pope. M. T .
tutti lwpo#y
Sprinaer-Vctlllg: New Yllftt. t98).
Chains
757
Ta5 + (78 pm) and the most c11mmon corresponding edge-shared p<llyanions are
(Vt 0 0:11l"- . (M<>,0: 4 1"-.
IW,Otvf - . (W70:..f'-. (Nb,0 111l"-. and
[Tllt,O,.,f-. 4s To form larger polyanions such as [W t:042)t: - or [H2 W t2 0.wJ"- . edge
sharing must sive way to apex sharing.
The isopoly anions may be considered to be portions of a closest packed array of
oxide ions with the metal ions occupying the octahedral holes. The edge-sharing array
found in (V 10QJ- consists of ten octahedra stacked
shown in Fig.
This
seems to be the largest stacked-octahedral isopoly anion cluster compatible with
metal-metal repulsions. and the remaining edge-shared structures represent portions
of this unit.4f>
However. explanations for growth limitation based on repulsion of metal ions may
be somewhat oversimplified. Elements other than vanadium . niobium. tantalum.
molybdenum. and tungsten do not form isopoly anions. Other ions which have
appropriate radii (e.g . AIH. 67 pm; Ga'. 76 pm; 17+. 67 pm) for discrete isopoly
anion formation instead form chains. sheets. or three-dimensional frameworks. Why
does polymerization stop for isopoly anions? An oxygen atom in a terminal position in
an isopoly anion is strongly " bonded to a transition metal such as Mol VII or W(VII.
These h:rminal oxygen atoms are never found trans to one another because they avoid
tc)
Ftg. 16.10 The slructures or e<lge-shared isopcly anions showing their relation lo the M,.,O""
structure: (a) M V; (b) M = Mo; (c) M Mo: Ill) M Nb. Ta. (From Kepcn. 0 . l.
lnurx. Clrem. t%9. 8 . 1556. untl Day. V. W. ; Klempere.-. W. G. : Maltbie. D. J . J. Am.
Chem. Sue. 1987, 109. 2991-J002 . Repro<luc:ed with
tGrneber. E. J.: MOtri.<un. 8 . M 1o c,.flulluxr. 51. 8 tm. JJ.
which has a structure analogous to (V..,O,.('-. weakened the validity or this
., The i<Oiation of
rct.Jtionhip .
.. Kepen. 0 . L. ln<>rx. Chrm. 1969,8. 15S6- t558.
758
161norgonie Choins, Rings, Coges, ond Clusters
competing for the same vacant 1'1Jt metal orbital. Instead they are found opposite a
bridging or internal oxygen. The effect is that the metal ion is displaced in the direction
of the terminal oxygen, away from the oxygen opposite it (trans effect), just as you
would predict based on a metal ion- metal ion repulsion model. Metal ions such as
Al(lll ) or Ga(JII) are poor n acceptors. Thus thei r terminal oxygen a toms are not
stabilized and can repeatedly attack ulher units to give continuing polymerization. The
terminal oxygen atoms of the transition metal polyanions, however, are stabilized by
n bonding and have less affinity for adjacent metal units. o7
Although elucidation of various molybdate species continues, four aPPear to be
most important: ( I ) the simple molybdate, MoOt. stable at high pH; (2) the heptamolybdate (also known as paramolybdate), (Mo70 : 4 )6 - (Fig. 16.10c), formed in
equilibrium with molybdate down to pH 4-.S; (3) octarnolybdate.
16. IOb);lll formed in more acidic solutions; (4)
the largest
isopolyanion known. present in solutions a1 about pH 1.8...., From strongly acidic
solutions can be precipitaied polymeric Mo0,.2H10 consisting of sheets of cornersha.r ed M06 octahedra.
The formation of isopolytungstates is similar to tha t described for the molybdates
a.l though the c hemistry is even more difficult. The simple tungstue. wo!- C.lists in
strongly basic solu tion. Acidification results in the formation of polymers built up from
wo6 octahedra. The nature of the tungsten species present depends not only on the
present conditions (e.g., pH) but also on lhe history of the sample since some of the
conversions are slow. Upon acidification of wo!-. "paratung:state A",,., (W70..,...] 6-,
forms rapidly. Its protonated form, (HW70,..)5- , has also been detected. 51 From these
solutions are precipitated salts of the dodecameric anion, (HzWt!042 ]to- (paratungstate Bl, whose framework is shown in Fig. 16. 11a. From more acidic solutions it is
possible to crystallize a second dodecatungsuue ion. (H 1W 110 40 ]6- ("met:ltungstate"). The structure of this ion, although built of the same W06 octahedra, is more
symmetrical, resu lting in a cavity in the center of the ion (F'tg. 16. 11b).52
In recent times many advances in isopoly anion chemist ry have been made by
shifting reaction chemistry from aqueous to aprotic solution. This can often be done
by employing a solubili7.ing cation such as tetrabutylummonium ion. For emmple,
when ((n-Bu)4 N)OH and ((n-Bu)4N IIH, V 1110:"1 :lre mixed in
a new isopolyvanadate fonns:53
+ JOH - -
2(V 50 t,J1 -
+ lH:O
(16.331
41 Pope. M. T. Hnrropoly and lsoJJQ/y OJWm<itJitJtrs: SprinGCrYcrlatl: New Yori<. t91!l .

.,. B01h o and 1J homer1 of (Mo,O.,,,J"- are known and isomcnz.c: intr:>molccular1y in solulioo.
W. G .: Shum. W. J. Ant. Cltttn. S<x. 1976., 9.Y.II29t-li29J. MaSlen. A. F.: GheUu. S.
F. : Brownlee. R. T. C.; O'Connor, M. J.; Wedd. A. G. ln<>rR. 01nn. t980. 19. 31166-3868.
Klemperet', W. C .: Schwam. C.: Wf'isht, 0 . A. J. Am.
S.>c. 19AS, 107, 694t-69SO.
B.; Pautat-86schen. I. Arta Crystanc,r., Sm. 1J 1981,18. 1710-1118.
JG Prior to any definite knowledce o ( the SlrucJUre 0t
o( the cmp;ricut (onnubl ol each of the
various panuungslaJe ions, they Wttt otbit0'1llity :>s.'iJIOCd tater IAbd uch
A. B. X. Y. ond z_
M'"'h e:wty c:oofusion in this r.dd occurred
wotkcn rcfetre\1 to "pai'Oltunsstate" without
l!pOCifyina which ol the many possible specie w.IS being 'ludie<l.
' ' CruyWI>Iftl, J. J. ; van dcr Muwc, t. F. J. J. Cht111. S<>c. V..lllttl Tnlfls. t9117,
S2 Althoop it mij;ht appellt th:u Ill< a similar. but s'""ltcr, cavity in the per.uunplllle B ion. the
van dcr Wonls radii of Ihe OA)'aCn atoms on the inner Dp!CCS cJ the OCIAik:dr:> (ormin& Ihe SIIUCture
e&ctivdy fill the c:1vily.
Day, V. W.; Klemptt. W. G.;
0 . M. J. Am. Ch"'' Sue. 1989,//l , 4JUI-Ut9.
Chain
,.,
7S9
Cbl
Fig. 16.11 The scruccures of cwo

dode<:alunascace isopoly unions ; (al che
B ion. [H,w 1, 0cJ'0 -; (bllhe mecacuniJiate ion. [H:W 1
[From
Lipscomb, w. N. tnot"IJ. Chrnt. 1965. 4, 132. Reproduced wilh pel"mission.)
,o...,r-.
This anion (fig.

is of spco;ial sicnilicance because it is the
uample of a
transition metal polyoxoaniun cage chac is built from
tetrahedra. In a
similar vein. relluxing (n Bu.NilH: V 100 2.J in aceconitrile leads co (MeCNCV 120d(Fig. 16. 12b) In which, remarkably. MeCN is found suspended into a
basket .S4
Undoubtedly we c.1n expect many incerescing and unusual isopolyaniuns to be
isolated and char.lclcrized in the
aheud . Th.: number o r praccical:lpplicalions for
is impressive and extends to medicine, catalysis.
these materials and their
and solid stale o.levices.D
,.,
tbl
Fig. 16.12 Scruccures o>f twu uxoonioM o(

prcr>:Jred from
sol.ents.
Ia) [v,o,.t' . tbi(CHlCNCV.,0,1( -. !The aceconiu ile molecule is sus.,.ndcd in chc baskcc
denoced by che symbol C . )(Frum Doy, V. W.: Kternpercr, W, G.:
0. M, J. An1.
SK. t989. Ill ,
and 59SV. kproduccd wilh permission.)
,. Day, V. W.: Kkmperer, W. G.: Yotci. O. M. J .1\m. Chtm. $. 1.98!1.111. S9j9-SII61 .

SJ
Pape, M. T.; Miller. A. J\111/tW. Chnrt. tnt, Ell. EnRI !HI, 10.
)4-.18.
760
161no rva nic Chains, Rings, Cages, and Cluslers
--
ng. 16.13 (al The Slructures of lwo heleropoly
1<1
12-trolybclophosphale or
12-tuncstophosphate. (b) and lc) Oe1ails of coordination of lhree MO. octahedr:l with
curner of the heleroatom tetrahedron.
He te ropoly Anions
one
It has been noted that there is a cavity in the center of the metalung&tate ion. This
cavily is surrounded by a tetrahedron of four oxygen atoms (Fig. 16.13) that is
sufficiently large to accommodate a relatively small atom, such as P(V), As(V), Si(IV),
Ge(IV). Ti(IV), or Zr( IV).S6 The 12-turcstoheteropoly anions)7 are of general formula
Analogous molybdoheteropoly anions ore Dlso known. For
example, when a solution conraining phosphare and molybda.te is acidified, the ion
(PMo 120.oo) 3 - is formed. Obviously phosphorus-oxygen bonds are nor broken in the
process so we can view the product anion as rhe incorporation of
into an
cage. Molybdoheteropoly anions of this type are of some importance in the
qualilative and quantitative analytical chemistry of phosphorus and arsenic.
Berween JS and 40 heteroatoms are known to form heleropoly anions and their
corresponding acids. Large heteroaroms such as Cee IV) an<l Th(l V) are found icosahe<lrolly coordinated in salts such as (NH.hH 6CeMo1:01 (Fig. 16. 14). 11 is unique
inasmuch as pairs of Mo06 ocrahedra share facts to form Mo1 0v groups which are
corner connected to each orher ..59
Of the many other hetcropoly acids, the 6-molybdo species are of some interest.
These form with heteroatoms Te(VI) and J(VII) and tripositive meral ions such as
Rhllll). All of rhese heteroatoms prefer an ocUihedrnl coordination sphere, which can
be provided by a ring or six Mo06 octahedral (F'I(I. 16. 1S). Note that formally lhe 6-
rt.<UIIing Jlrucu..e, which hDs TJ symmetry, has tome Ia be known as the Key(lfin structuu.
named Dl\er its discO\ICror.
$6 The
!fffix 12 nuy be Ltled lo reJ*oce lhe more wmbcnomc: "dodcea"to indieale the ma'nberof
mOb! ;uom octahcdr:J
to lhe hel..,..om.
J1 The
"'One or more protona may be all\ud 10 the Mioo wilh ecrrcspondina ffiklction of anionic ell..
"'Dexter. 0 . 0.; Silverwn. J. V. J . Am. Cl,m. $. t968.110. J.S89-)S90.
Chains
Fig. 16.14
of the
howing the
MoO. OCluhet.lra.
761
sketch
ion
of the
heteropoly formulation can be awlied to the heptrunolybdate species discussed earlier

if the seventh molybdenum atom is considered to be a pseudo-hcteroatom. At one
time it was feh that the 6-heteropoly acids should be isomorphous with the hcptamolybdate. This is not the case as may be seen by comparison of Figs. 16. t Oc and
16. IS. The structures are morr similar than might be supposed, ho-ver, the principle
difference being whether the heterootom is SUrTounded by a planar ring of molybdenum atoms 16-heteropoly species. Fig. t6. 1611) or a pudcered ring (hepta1110lybdate,
F.g. 16.16b). 'There are also more complicated heteropoly acids. including dihcteropoly acids such as
which hns been found to have structure
(sometimes c:1lled the
structure) related to the 12heteropoly acids (Frg.
16.17).
As a class, the isopoly and hctcrpoly anions otTer several interesting fucets for
study.60 'They may be considered small chunks of metal oxide lattices. As such they
provide insight into catalysis by heterogeneous oxides, an approach that is currently
enjoying strong interest for selective oxidation of organic molecules. As anions they
show very low surface charge densities :lnd low basicities. For exan1ple. we generally
think of the perchlorate ion. Cl04 . as having a I'<'Ty tow basicity. One study has shown
that the hexamolybdate(- 2) ion and 12-tungstophosphate( - 3) ion have lower
basicities than perchlomte. and the
3) ion is only sli8Jltly
rich coordination chemistry is evolving
more basic th;m perchlur.ue.r
Fig. 16.15 'The ,;rruclure of

the 6-molybdotellurote
anion, (TeMo.O,.I"(Achlpted. in pnrt. from

Kepert, D. L. PmR. /1'101'1.
C/rrm. 1965. 4, 199.
Reproducc:t.l whh
permission. I
eo Day. Y. W.;
W. G. SO,nu t9115. 1U. $))-S4t .
&r=. L; Pope. M. T. J. 1'11p. Clltm. t9?5, 79, 91-93.
762
16 1norvo nic Choins, Rings, Coges, ond Clus1en
II
(b )
Fig. 16.16 (a( Ptnnar ring of Mo nloms surrounding

in
(bl Puckered rins of Mo ntoms surrounding sevench Mo acorn in (Mo,(h.!"-.
acids.
II )
lbl
(C)
Fig. 16.17 Relotion belween lhc Slruc:lurcs or 12-helcropoly und dimcric llheleropoly :acids:
1al lhc (Pw,o..,J'- aoioo (see Fig. 16. 13): (bl 1he tPw.o,.),_halr-unil rormed by removal or
shnded occahcdra (rom (a); (c)
dimeric
ion rormed rrom IWO halrunils. Ib).
(From Wells. A. F. Slmclura/lf10f11ottic'
Slh cd.: Oxford
London.
19116: p S22. Reproduced wilh pennission .l
in which many polyanions have been shown to function as

In some instances the cation simply binds to bridsing or terminal oxygen atoms founcJ on che
surface of the polyoxometnlate anion. For
Mnz+ binds weakly to a lermin;ol
oxygen atom of [H2 W 12 0.aoJ"- : thus che anion functions a
ligand. If.
however. che polyoxomet3late anion has
creutc:c.l by missing mcc:d unics
1Fis. 16. t81. coordination may occur hy incorporaling the cation inco chc vacancy (Fig.
16.t9) . Polyoxometalate structures with vacancies are referrC\1 to as lur:11nnry (a space
has been omitted) species. These species may function as peni:Wenwhere
l:lle ligan..ts (e.g.. six-coordinate Co in [(SiW 110)9 >CoC H20ll"- > o r telradent..'lte
ligands (e.g., four-coordinate Cu in [(PW
All facets of s tud y have been greatly aided by the ease wilh which crystal
slructures may be obtained and by the availability of sensitive Fourier transform NMR
93
spectrometers which allow nuclei such as 170,
Nb, ..,Mo. an..t 1113 W to be used
rur structural studies. Oxygen- 17 NMR spectroscopy
prove<.l lo be particularly
useful because 170 chemical shills are very sensitive to environment. As a rcsull it is
to distinguish between lerminal and various kin..ts of bri<lcin11 oxygen sites.
Tbe 170 spectrum of [W60 19] 1- and its strvclurc a.r e shown in Fig. 16.20a.'-' We see
''v.
.: Pope. M. T.; Mliller. A.

Clwm. Int. EJ.
111'11 . JO, l4-18.
V. W.: Klanperer. W. G.
1985. 211. Hl-5-41.
Chains'
Fig. 16.18 Examples of lhc

IXM 11 0,,l and lhri:C
.aruclures formed 1callco.l bcunnry
me1al fl':ll!fi\Cnls. !From Pope . M. T.; MOller.
34-ll!. Rcproo.luced wi1h permission.!
763
cr[XM,10,0 1n- ion losing bolh ono: mcaul

!isomers A XMvO..., and 8-XM,O,.). The
have
silcs which C3n be filled by olher
A . Anll""'
lm. Ed. Enx/. 1991. J(),
Cpr.O,
n.
---\.:::/iCp
---"
Rx::.___
(SsnR
Fig. 16.19 The la.:unary polyoxomeullole ligand. XM 11 0>v re"eling wilh vuricly ur Lewis
acicJs. (From Pope. M. T.; Muller, A. An).'t'll'. Chmr. lm. Ed. EnJI/. 1991. JC. 34-)H.
Reproo.luecd wilh permission. I
764
16 lnorgonic Choins, Rinvs, Coges, and Clusten
(I)
__ , . __
_.
400
6(n01
(b)
Fig. 16.20 "o NMR spectrn or (a) [W6 0 19f - o.nd lbl ((CplTi(W,O,aJJ'-. labels on spcctrdl
lines indic3oe assi&nments: line a to site A. tine b to site B. etc.: - impurity. [From Dy.
v . W. ; Klemperer, W. G.
1985,228. S3J- S41. Reproduced with permission.]
one: signal (b) for the twelve bridging

atoms. one signal (n) for the encapsulated
oxygen, and one for the terminal oxygens (c). The organometallic derivative
3
((CpYfi(Ws0 11J] - gives a spectrum (Fig. 16.20b) considerably more complicated.
Now there are six different kinds of oxygen atoms, each giving rise to a separate
signal . but by comparison to the spectrum or [W60wl 2-, reasonable assignments can
be made for terminal oxygens E and F, encapsulated oxygen A, and bridging oxygens
C and B. The remaining signal is assigned to the D oxygens.
It can be only mentioned here that isopoly and heteropoly anions also give rise to
highly colored mixed oxidation state species: the tungsten bronzes64 and the heteropoly blues."'
6<
..,
Whittingham, M. S.; Dines, M. B. Surv. ProR.

198t. 9, 66-69
Y.: Lauroay, l . P.; Seid Sedjodi. M. A. f fl()rg. Clomt. ttae, 19, 29lJ-29JS.
N.: Gomez-Romero. P.: Jamescn, Ci. 8 .; Balter, l- C. W . J. Am. Cltrm. Soc. 1991. IIJ,S658-S663.
Rings
765
The most important ring system of

chemistry is th e benzene ring. either as a
separate entity or in polynuclear hydrocarbons s uch us naphthalene, anthracene, and
phenanthrene . Inorgan ic chemistry hus two (ot least) aoologues of benzene: born7ines.
B3N3 R6 and trimeric
compounds. P3N3X6
Bora1ine has been known since the pioneering work of Alfred Stock early in this
century. Stock's work was important in two regards: He was the first to study
compounds such as the boranes. silanes. and other simila r nonme1al compounds. and
he perfected vacuum line techniques for the handling of nir and moisture-sensitive
compounds. invaluable to the modern
chemist.67 Stock synthesized
borazine by heating the adduct of diborune and
3B1 H6 + 6NH 3
2B 3 N 3H 6 + 12H1
->
(16.34)
More efficient synthesis are:69
NH 4 0
+ BCI3
0 3 B3 N 3 H 3
NH4 0 + NaBH4
B3 N 3H 6
83N 3H 6
(16.35)
+ H 1 + NaO
(16.36)
N- or B-substituted boratines mny be mode by appropria te substitution on the starting

materials prior to the synthesis of the ring:
(RNH 3)C1 + B0 3 or substitu tion afte r the ring
0 3 B3 N 3 R3
H 3 B3 N 3 R3
(16.37)
formed:
(16.38)
Borazine is isoelectronic with be.n zene, as B-N is with O=C. (Fig. 16.21). In
physical properties. borazine is indeed a
analogue of benzene. The similarity of
the physical properties the alkyl-substituted derivatives
benzene and borazine is
even more remarkable. For example, the ratio of the ubsolute boiling points of the
substituted born7incs to those of similarly substituted benzene is constant. This
simila rity in physical properties led to alabelina of boruzinc as "'inorganic ben7..ene."'
This is a m isnomer because the cilttmiC"III properties of bor.u:ine un.l b(n7.cne are quire
diJfc:rent. Both compounds have aromatic 1T cloulls of e lectron density with potential
ov.:r all of the ring atoms. Due to the difference in
for
between boron an.! nitrogen. the cloud in bomzinc is ""lumpy""
more electron
or
or
of /ntKgDnic Hiey Syllmu;

R.. Ed.: Elsevier: New York. t9'1.!. Wollins,
J. 0. NnnMtta/ Riflt:S. Cagu attJ C/11sttr1; Wiley: New Yclf'k. 191!8. Haiduc. 1.; Sowcrby, 0 . 8 .
Clnoisrry of lmvgonic Homo anJ
Academic: New York. 1987: Vols. I and 2.
Heat. H. G.
lnorgonic Hcttrney(/ic
N/trlJIItn anJ Ph<lspho"'s: Academic:
New York. 1980. Ma.u ey. A. G. Muln Grtlllp Clmristry: Ellis Horwood: New Yclf'k. t990.
01 See Shriver. 0 . F.
Mun/p<1/uti01t of
C<>,pnllnJI: Mc:Gn>wHill: New Yclf'k, t9&J,
and
0rRGIHHftttol/ic CJrnistry; Woyda. A. L ;
M. Y.. Eds. ; ACS
Symposium 5mes 357: American Oemical Soeiccy: Woshi,..ltJn. DC. 1985
.. SIOdt. A. ; Pctltand. E.
Brt'. lfl6.s9. 2215. Sloct. A. Hydrl<ksof&xonwwSilkOII;Catnd
University: New Yclf'k. t91}.
09 Benzine synJhcses an: mliewccl in Gnw,.,. HontJIH.tlt Vtr
Sp<incCS'Valloa:
New York. 19711; Vol. 17.
66
766
16 Inorganic Chains, Rings, Coges, and Clusle ....
ufpn
HVH
II
JiyH
H
11
cbc
Fig. 16.21 Electtonic SJtuclurcs of(a) benzene; (b) bor:Wne .
.Jensity is localized on the nitrogen ruoms (Fig. 16.!2).1'0 This partial localization
weakens the ,.-bonding in the ring. Eaoh nitrogen receives more a-electron density
from neighboring boron than it gives awo1y as a
'Jlle net effec.t is that the
churse density on nitrogen increases. In a.Jdition, nilrogen retains ils rosicily and
boron its acidity. Polar species such as HCI can therefore attack the double bond
between nitrogen and boron. Thus, in conlrast to benzene, borazine readily under.gocs
addition reactions:
H
'-N<"" ' N /
II
+JHCI
(16.39)
H/ ' N / '-H
0
10
+ HCJ -
No reaction
Boyd. R. J.: CIIoi. S.C.; Hale. C. C. Clomt. l'lty'- Ll'll. 1* . 111,

J . C. J . Am. CMm. SM. 1991, r1J.ll9l-l:MI.
(16.40)
Fink. W. H.: Ridlards.
Rings
767
II
Fig. 16.22 ConJOUr map of 1he chlltl;C den:w y in !he mo.>lecular plane of (at ben7..ene
(b) bor:lrine. [From Boyd . R. J.: Choi. S . C.: H3te. C. C.
l'hy. L-11. 1984. 111.
t36- t4 1. Rc:procllced wilh permis.otiun.l
The COillrasting u:ndcnccs of the rvo compounds toward atldi1ion vs. arumwic
substitution is illustrated by their
with bromine:
H
H
'NI""" 'N/
U
8
8
H/ ' N / '- H
+JBr. -
.
.
.
0 -
(16.41)
()Br
I
(16.J2)
""""
llle elecrronic
between b<:nzcne und bora7Jne is further supported by
the pmpenies of compounds of the type (R.,B)N)ICrtC0) 3 All hough the.\e are formally analogous to 1'1"-C.,R.,)CrtCOh. the handing is not near1y so strong in the
bora7Jne complex-its ring-metal dis.,oo:iutiun energy appears to be about one-half
rhat of the arene complex. In uddilion. rhcn: is considc:r.. blc: evidenc:e that the bora7Jnc
molecule is puckered in rhesc complexes.? The actuul structure appe-Jrs to be intermediate between a true 1r complex ano.l the extreme u-only model:
71
Scoui, M.; Valli...,..,..., M.; Gant. R.: Wcm<:r. H. J .
CltrHJ. tfiS. .!81>. Jw-11)(>.
768
161norgonic Choins, Rings, Coges, ond Clusters
'
'
N - a/
R-a/ C) 'N-R
/
/N- -a,
1
R
Cr
R
c. . . . cI 'c0
0
aorazine analogues of naphthalene and relaled hydrocarbons have been made by

pyrolyzing borazine or by passing it through a silent discharse. Related four-memR2 a 2 M1 R2. and eight-membered rings, R4 a 4 M4 R, are also known, but
bered
considerably less work has been done on them than on boraz.ine.
Renewed interest in boraline derivatives has resulted from their possible application as precursors to boron nitride ceramics. For example, the inorganic analogue of
styrene. (H 2C=CH)a3N 3Hs, has been polymerized and decomposed to produce
BN.n
+---c-c
H
I I
'- ..,...a...._ H..,....H
IQI
,...a,
..,....s,H
H
N
IOOO'C
aN
(16.43)
aoralines have the correct B-to-N ratio for the production of this ceramic and its
polymeric precursor may be used to deposit a uniform surface coating.
Benzene may be hydrogenated to produce the saturated compound cycfohexane.
Hyurogen:uion of boraline results in PQiymeric materials of indefinite compositions.
Substituted derivatives of the saturated cycloborazane, a 3N 3H 12 form readily by
addition to borazine (Eqs. 16.39 and 16.41), but special techniques are necessary to
prepare the parent compound. It was first synthesized by the reduction of the chloro
derivative:
2B 3N 3 H., + 6HCI---+ 2CI3 B3N 3 H 9
&N.aH,
2a3N 3 H 12 + 3B 2H 6 + 6NaCI (16.44)
n Lynch . A. T.; Snedden, L 0 . J. Am. Cll<'m. Sue. t989. Ill, 6201-621J9. Boron nilridc exists In two
forms, one analogou.s 10
ancllhe other 10 diamond. The graphi1c rorm hus laycn in which
the boron oJoms lie above nitr<>&cn otoms in !he lay.:r below. Although this malctial shares with
gruphitc the propcny of being a lllbricant. unlike lf3Phite, it b an electrical insulator. The ctJbic
form. second only to diamond in hardness, is an ec:c:l!ent syn1hctie abr.lsive.
Rings
769
lsoelectronic with bora7jrK is boroxine, H 3B30 3 It can be pr-oduced by the

explosive oxida tion of
or B,H 9 Bo roxine is planar but has even less .,. delocali7.ation than boraline. It is also less stable. decomposing at room temperature to
diborane and boron oxide.
A boron-phosphorus analogue of borazine has been synthesized rather recently. 73
The electronegatitives of B lllld Pare similar. unlike those of B and N. As a result.

polarization should be less extensive in this compound than in boratine. The B3P3 ring
is planar, with equal BP bond lengJhs and shortened BP bonds, suggesting significant
aromaticity. Even more recently the boron of bora1Jne derivatives has ben replaced
with aluminum to give "aluma7..enes. " 7
Phosphazenes7S
Early workers no1ed the extreme reuctivity of phusphorus pentachloride toward basic
reagents such as water o r ammonia. With the former the reaction is reasonably
straightforward. at least for certain stoichiometries:
+ H 10
P0 5 + 4H1 0
P0 5
OP0 3 + 2HO
(IUS)
H 3 PO + SHCI
(16.%)
For reactions with ammonia analogous products such HN=zPCI 3 ami

were proposed. but characterization was hampered by incomplete reactions. separation-resistant
sensit ivity to moisture. Furthermore, gradual polymerization occurred with klll.\ of ammonia 10 yield "phospham". a poorly chur..:terized solid
of approximate formula (PN2 HJ,, us the uhimate product. If instead offree ammonia its
less re:.tctivc conjugate acid is used. reaction with PCI5 proceeds at a mO<lerute rate
und the results are more tlefinitive:
NH4 Cl + PelS
...'"'"
CHCt,ciiCI:
"PNCI!"
(16.47)
If the product were u monomer. its strocwre could be drawn as CI.Ps=iN, which is
analogous to organic nitriles. R-CEZN. For this reason the origincl names used for
these compounds were phosphonitriles , phosphonitrilic chloride. etc. However, the
products are acwally either cyclic or linear polymers of general formula
Thus. by analogy with benzene. bora7lne, e tc .. these compounds have become known
as phospha7.cnes. The mojor product of the reaction in Eq , 16.47 and the easiest to
"Oi:>o. H. V. R.; Power. P. P.
Int. Etl. Eiv/1. lft1.16, 1270-1271. Dias, H. V. R.;
Pow..-. P. P. J . A Cfltm. Soc. 19119. Ill. 144-1411
.,. Wqaoncr. K. M.: Power. P. P. J. Am. C'ltl!t'lf. S. lli'JI. IIJ. ))15-))9).
" Alcock. H. R.
WnlpoiiiNis; Ac:adaric: t-kw Yoc1t. 1972.
770
16 Inorganic Choins, Rings, Coges, ond Clusters
sepnmte is the trimer, 11 "" 3. Smaller amounts of the tetrnmer and other oligomers up
to n = 8 have been characterized and higher polymers exist as well (see below).
Analogous bromo compounds may be prepared in the same mnnner. except that
bromine must be added to suppress the decomposition of the phosphorus pentabrom.ide:
(16.48)
(16.49)
'llle fluoride must be prepared indirectly by fluorination of the chloride:

(NP01 ) 3 + 6NaF
---+
[NPF1) 3
+ 6Na0
(16.50)
The corresponding iodide is unknown, but a phosphazene with a single phos-
phorus-iodine bond. N 3CPCI!l:!P!R)I. has been reported .7'

The h;tlide trimers consist of planar six-membered rings (Fig . 16.23).n The bond
angles are consistent with spl hybridization of the nitrogen and approximately .tpl
hybridization of the phosphorus. Two of the spl Ol'bitals of nitrogen. containing one
electron each. are used for a bonding and the third contains a lone pair of electrons.
This leaves one electron left for the unhybridized P: orbital.
The four spl hybrid orbitals (housing four elearonsl of phosphorus are used for a
bonding leaving a fifth electron to occupy a d orbital. As shown in Fig. 16.23.
resonance structures can be drawn analogous to those for benzene indicating aromaticity in the ring. However. the situation is more complex than these simple resonance
structures indicate. The planarity of the ring. the equal P-N bond distances. the
shortness of the P- N bonds, and the stability of the compounds suggest <lclocalization. However. not all phosphazenes are planar. ;on<l the absence of planarity does not
appear to make them any le!IS stable. Funhcm10rc. the phosphazenes yicl<l UV
spectra unlike those of aromatic organic compoun.Js an.J they ure much more <liffi.:ult
to re<luce. Thus the extent of ddoc-..Jization and the nature of the aromaticity have
been debated for years. Unlike in benzene .,. bonding in cyclophosphazenes involves
J and p orbitals. There have been several descriptions offered for such J,.-p .. bonding.
Craig and Paddock suggested the following model:"''llle J
of the phosphorus
atom overlaps with the p. orbitals of the nitrogen atoms a<ljacent to it <Fig. 16.24a). As
a result of the gerade symmetry of tlle.d orbitals. an inevitallle mismatch in the signs of
the wave functions ocwr in the trimer (see Fig. S. IOI resulting in a node which reduces
the stability of the delocalized molecular orbital. The Jy: orbital. which is perpen-
Allcock , H. R.: Honis, P. J. III<XJ:. Cltcm. t9HI , 1/J, :!1144-211-18.

deviations from plnnarity found for the chloride. bromiclc. Mol Ouoridc may he the rcult of
packing effects. The P- N boncls appear to be llc:xiblc nd angle changes tcad h> lillie tal>ility loss .
TT SmuU
.,. Paddock, N. L. Q. &v. CMm. Soc. t964. /8, lf>ll.
Rings
Cl
Cl
.........
II
Cl
Cl
-:;:?''
I_;-
Cl
"/
771
Cl
,.,
(bl
Fig. 16.23 Suuclure of crimeric phosph:ucne. P,N,Ct..: (al c:C>nlribucinr;: reson:onc.:

scrucrures: (b) molecular scruccure as lldermined by X-r.ay dilfr:lclion. (From Bullen, G. J. J.
S. (AI 1, 1, I4SC. Reproduced wich permission.)
dicular to the dr.:. can also over1ap with

P: orbitals of nitrogen. but in this case no
nodal surface results (fj;. 16.24b). 'There may also be in-plane,.. bonding between 1he
spl nonbonding orbital o r nicrogen and the d6 Y and/or dr-y orbitals of phosphorus
(F'rg. 16.24c.d).
lbl
<:Z:Y3
1<1
Cdl
Fig. 16.24 Theory of CniJ and Paddock (or 1r booldiooa in phosph:uenes: Ia) inCer.>cJion of
p ,!Nl and d,.IP): (b) iootenccion or p,INI and d,..CP); (c:) hocerac:tion of sp"(N) and d..(Pl:
ldl in1eraclion or .rp>(N) :>nd d,:._,:(P). (From Cor1>ti D. E . C. l'hosph,..s; Elsevier.
AmsteriiAm. 1978; p 2lS. Reproduced wich permission.(
772
161norgonic Choins, Rings, Cog.., ond Clusters
Fig. 16.25 Theory of Dewar for " boo<li1111 in phospllaz.enes: (a) lhe relation of the
orthoGOOal phusphurus do and tJ ortilllls 10 the nitroaen P: orilitals as seen perpendiaJiar and
panllcl 10 the : :uis. respecci,.ely; (b) the thr<o:nter bond model ror P,N)O,. [From
Schmulbach. C. D. l'mt:. lnorg. Clum. I HS. 4.
RepJodUttd with pennission.)
ru.
Dewar and cowortet"s offered an :llternative view.79 (n their model the d,. and d,-.
orbitals are hybridized Lo give two orbitals which are directed toward the adjacent
nitrogen atoms (Fig. 16.2S). This allows for formation of three-center bonds about
each nitrogen.so This scheme. sometimes c:llled the ..island .. model. results in deloc:ilintion ove.r selected three-atom segments of the ring, but nodes are present at
each phosphorus ::11om since the two hybrid orbit:lls of phosphorus are orthogonal to
each other. Evidence has been offered in support of both models, but neither theory
has been confirmed to the exclusion of Ihe other . A third viewpoint holds thai d orbillll
panicipntion is relatively unimportant in the bonding in these molecules.
The structures of tetrnmeric phosphazenes are more flexible than lhose of lhe
!rimers. The structure of
is planar, but others are found in a variet y of
conformations (tub, boat. chair, crown. saddle, and struct ures in betwee.n). The
particular structure adopted is not very predictable and suggests that intermolecular
forces play a major role. The telrnmeric chlorophosphazene has been isolated in two
forms (Fig. 16.26),111 the most stable of which assumes a chair arrangement (sometimes called the T form). The other form (metastable K) has a tub conformation. An
interesling feature of these compounds is lhat the nonplanar structures do not mililate
extensive delocali7..ation in the rinas. The corresponding organic compound.
cyclooctatetracne. CRHR, is nonaromatic for two reasons: (I) lis nonplanar. chair
structure precludes efficient p,.-P,. overlap; und (2) it does nol obey the HOckcl rule of
(4n + 2)1r electrons. The Hilckel rule was formulated on the basis of p,.- p., bonding
and holds for cyclic organic compounds from n I (benzene) ton = 4 l( 18)annulene).
The use or d Of'bitols removes lhe restrictions of the HOckel rule and :llso allows
greater flexibility of the ring since the diffused orbitals are more amenable to bonding
in nonplanar syslems. Both the Crnig!Paddock and Dewur models predict that the
,.. Dewar. M. J. S.: l..u<:ken. E. A. C.: Whilchc.a d, M. A. J.
Soc. 1960. 242)-2429.
'"' See paae 791 for D diiCIJ..SiOII or lhrec-ccnler bondin&.
G. J. Am. C"""'
IJ86. /08, 568-571.
Kl"isnanlmhy, S. S.; Sau. A. C.; Woods. M. AJv. lnorR.O trm. RadiMm. 1973. Jl. 41- 112.
1 1 Trinquicr,
Oil
Rings
773
< PeNIP: s 1)4
lbl
(OJ
16.26 Structures ol telr:lmeric pho$1lhazene. P.N.CI.: (al 1ub conrorm:uion: tbl chair
conrorrnation. [Structure (aJ rrom Hazekamp, R.:
T. ; Vos. A. Actu Cr;rstartnt:r.
1962. U, SJ9; SII'Utt ure (bl rrom
A. J.:
A. A.ttu Cr;rstonuRr. 1968. U , 101.
tetramer is stabilized by deloc:alization (unlike

3nd the stabilization
is eithet' equal to (Dewar) or more thun (Cruig/Pllddock) that of the trimer.
Our discussion has dealt with trimeric and tetromeric phosph:lzenes. but many
other ring sizes h3ve been synthesiuc.l. For U3mple. nil of the compounds,
(n .. 3- 121. rove been studied
Furthennore. the first cyclodiphosphazene has been prepared:""
(i-Pr)1N....._
(( i-Pr',_,. . -
I . .. .c
Ci-Pr):N /
P= N
I/
N(i-Pr)l
'
Nti-Pr)1
N=P
were long thousht to be too
(16..51)
for isolation because of ring
stmin.
Phosphaxene
Polymers
Phosphaunes can be polymerized and in many inst;mces their polymers have advantages over the cnrbon-based polyolefins and polyesters.' However. commercial
application is not as well developed as for the silicones cR 2Si0)". (see page 749). Early
studies were hampered by the sensitivity or the phosphorus-chlorine bond to
Oakley. R. T.:
S . J.: P:>d<lock. N. L ; Troucr. J. J . A,... Clltm. Sc><. t9!15. 107. 692l-69l6.
"' Bacciredo. A.: lkrtr:>nd. G.: Ml\i<>r.ll . J .P. ; S'crd . G.: Juud, J.; Gilly. J. J . Ani. Chrm. Soc. t984.
/06 , 6088-60811.
10
"'/MNJIOnic aJKI 0ri(QIIU..wtullk l'olyn...,..; Zeldin. M.; Wynne. K. J ,; Alk:.oclt. H . R., Eds. : ACS
Symposium Series .360: American Ocmical Society: Wo.shif'cJon, DC. t988. Mal1c, J. E.; Alk:od<,
H. R.; West, R.
l'ol1"'tn; Pn:111icc-HoM: EnaJewood O ifTs, NJ. 1992.
77 4
16 Inorganic O.ains, Rings, Cages, and Ousters
moisture. However. it has been found that trimeric chlorophosphazene can be polymerized thermally:
(16.52)
If this is done carefully, extensive cross-linking does not take place and the polymer (n
= 15.000) remains soluble in organic solvents. The reactive chlorine atoms are still
susceptible to nucleophilic attack and displacement:
[PNCI!),. + 2nNaOR -
[PN(ORI:!l.. + 2.rrNaQ
(16.53)
[PNCI:J., + 2nR2 NH
[PN(NR2)2)n + 2nHCI
(16.54)
--+
By varying the nature ofthe side chain. R, various elastomers. plastics. films. and
fibers have been obtained. These materials tend to be flexible at low temperatures, and
water and fire resistant. Some lluoroalkoxy-substituted polymers (R a CH 2CF)} are
so water repellent that they do not interact with living tissues and promise to be
in fabrication of artificial blood vessels and prosthetic devices.
Although the hydrolytic stability of some phosphazene polymers makes them
attractive as structural materials. it is possible to create hydrolytically sensitive
phosphazenes that may be useful medically as slow-release drugs. Steroids. antibiotics, and catecholamines (e.g . dopamine and epinephrine} have been linked to a
polyphosphazene skeleton (Fig. 16.27) with the intention that slow hydrolysis would
provide these drugs in a therapeutic steady state.'"'
Materials containing an inorganic polymeric backbone often have useful electrical, optical, and thermal properties. In addition they are being explored for
as
precursors to ceramics. One way to alter the properties of a polymer is to make
changes in the backbone. Recently. Mooner an.J Allcockll71rave shown that a C-CI
group may be substituted for one of the PCI, groups in (PCI.Nh 10 give a ring that
forms a polymer with carbon in its
(16.55)
This polymer is the first example of a poly(carbophospha7.enel.
,.. Allcock. H. R. In RlfQIS. Ou.f /n.t, o11J Polym<..-s u[ Mu/11 Grnup

Cowley, A. H .. Ed.:
ACS Symposium Series 232;
Chcmicul Society: Washington. DC. 1910.
M7 Mon-. 1.: Allcock. H. R. J. Am. Donn. Sue. t989, I /1, 5418-541!0.
Rings
(ol
ns
(b)
(C)
ng. 16.27
phosphazeno:s; tal steroidbooncl: (bl sulfadiazineboxtnd:
(.:) catecholamine-buund. IFrom Allcoclc. H. R. In Rinl(s, Cfusttrs, unJ Polymn of tM Main
Cro11p Elmtnrs: Cowley. A. H.. Ed.: ACS Symf!O'Iium Series ln; Amuic:ua Chemical
Society:
DC. 19113. Used with
Other Heterocyclic
Inorganic Ring
Systems
The reaction of
wilh ' "'Jier :u elevated temper.uures gives polymeric
!Eq. 16.23 ). but if hydrolysis is carried out al room temperature, the
mixture which resulls also
cyclic siloxancs. (Me1 SiO>. (n '"' 3, 4, etc.).
Me
\ I
Me
Ji- o,
Si
Si
Me...._ I
Me,...
_....Me:
I ' Me:
+ etc.
(16.56)
'o- s!
I \
Me Me
The trimer
a chair structure
to cyclo hexane and the tetramer has a
crown structure analosous lo
In the previous section we saw that cyclophospha:z:cnes could be turned inlo linear polymers thermally. The same is true for
siloxanes. In order lo achil:ve high mu(ecu(ar weights (lhe prO<Iuction of silicone
rubberl\), very pure cyclic tel ramer is heated with a trace of base (KOH):
(16.57)
776
16 1no r gonic ChoinJ, Rings, Cogn, ond Cluste"
Fig. 16.28 Oillgnmmatic

ollhe
metasilicaJe unions: (:1)
trisilicnte.
(b)
heusiliaue. (Si,.0 10) 11 SII'UCIUr"
rs;,o.r-;
Polymeric chain, band. and sheet silicate structures have been d iscussed previously (page 7421. and it should not be surprising to learn that cyclic silicate anions,
such as (Si30.,)'>- and (Si6 0 18) 1l- (Fig. t6.28) are known. 1llese anions are sometimes
referred to as metasilicates in line with the o lder system of nomenclature, which
assisned urtho to the most fully hydrated species (as in "orthosilicic acid." Si(OH)4 )
and
to the acid (and anion) from which one mole of water has been removed
(either in fact or formally; for example,
acid ,"
lsoelectronic with cyclic silicates are cyc:lic metaphosphates. The simplest member of the series is the trimetaphosphate anion, (P30 9) 3 -. The tetrarnetaphosphate
anion. [P.od-. is also well known. By careful chromatographic separations of the
glassy mixture of polymeric phosphates and metaphosphates known as Graham's sat t
it is possible to show the existence not only of tri- and tetrametaphosphates. but also
hexa- .1111 hepta-, and octametaphosphates. The
is effected and some
qualitative knowledge of structure is gained from the fact that two factors play :1 role in
the mobility of phosphate anions: (I) Higher molecular weight anions move more
slowly than do lower members of the series; and (2) the ring or metaphosphate anions
move more rapidly in basic solution than do the straight-chain anions of comparable
complexity tFig. 16.29).
In progressing from silicon to phosphorus, the increase of one in atomic number
results in a corresponding decrease of one per central atom in the anionic charge of the
rings. Further
from trimetaphosphate to sulfur trioxide results in a neu1ral
molecule. trimeric sulfur trioxide. This form is known as
and is isoelectronic
and isostructurat with the analogous trimetasilicate and trimetaphosphate anions. It
exists in a chair form and is thermodynamically
with respect to two other
rurms: fl-S03 which consists of infinite chains. and oS03 , which probably consists of
infinite
by cross-linking. Traces of moisture convert the 1"S03 form into
the a-S03 and P.,S03 forms.
Compounds which contain sulfur- nitrogen rings were known in the last century.
but many new ones have been prepared in the last decade . It is currently an area of
considerable interest. The ammonolysis of sulfur monochloride.
either in
solution in an inert solvent or heated over solid ammonium chloride. yields tetrasulfur
tetranitride:
.,..so,
(16.58)
"" The name hcxaJUeCaphosj:>hate has coUKd corlusion o - lhe years. On the basis ol erroneous
rtll..,jl'll cono:mifla lhr nnlUfC d double Slllls. Jhe Jelm
was assV>cd 10
Grzlam's salt of empirical composition NnPO> II hos abo bee" npplled 10 Ihe rdaled conunercia1
product !Clip) in which Ihe Na/ P r.llio is t: I. The lnH: metnphesph:lle a>nt:lino :. twdvemcrnttcRd
rina :.nd is but a wry minot componcnl or t he mixture known as
salt.
G"""""'
Rings
1n
'
'
Fig. 16.29 Sep3r.11ion o( pol)'l)hosphale anions by paperchromaiOil"IPIIY The ions are first
aUowed 10 migr:ate in a basic
and
in an acidic sol.ent. The straightc.hain pctyphosphales lie on the a.scendina br:lnch o( the y : the metaphOsphaleS on Jhe
lower bnnch. (From Van W:u.er. J. R. l'lto3plo<Jn,s and Its Cuf111XH1nds; Wiley: New Yorlc.
19.SS; Vol. I. p 702. ReprO<luced with permis,ion.)
11le product is a bright ora11ge solid insoluble in water but soluble in some
solvents. Although the
are reasonably stable to aliiiCk by air. they are
sensitive to shock or friction.""
A few moments' reflection will show that it is impossible to write u simple l ewis
stnteturc for s.N. Furthermore. the Cal!C struct ure I Fig. 16.30) hus been found to
have two pairs of nonbonding sulfur atoms at u
of only aboul 2S8 pm.
considerably shorter than the sum of the van der Waals radii 1360 pm). Although this
is longer than the normal S-S bond length (206 pm). some interaction must
occur between the transannular sulfur atoms. All of the S-N bond disances within
the ring are approximaJely equal ("'162 pm). indicating extensive delocalization (1211'
electrons) rather than alternating discrete single and double bonds. 1lle situation is
simila r to but more complicated than that of the cyclophosphazenes.
We have seen that S2N 2 and (SN).. c:1n be prepared from S4N 4 Other neutral
binary sulfides may be obtained from it as well. When S4 N4 is heated under pressure in
a solution of CS2 containing sulfur. S4 N 1 is formed. This molecule has a "half-chair"
conformation (F'tg. 16.31).90 Others such as S5 N6 and S 11N 2 have also been reported.
"
A. J. lnorr- Sytlllo. 1971. 17, 19?-t99.
"'O!iven. T.; Cocldinl. P. W.; Oakley. R. T. J. O.rm. Sue. C/km. Cummun. mt . 584-.SSS.
778
161norgonic Choins, Rings, Coges, ond Ousters
(3(
Fig. 16.30 Eight-membered sulfur-nitroaen rings: (al molecular structure of" S4 N 4 ; (bl
diagrammatic structure or N.s.F. illustrating alternating bond lenl)hs. [From Sharma. B. D.;
Donohue , J. Acta Crystul/ugr. 1963, /6, 891. Reproduced whh permission.I
Fig. 16.31 MOlecular
Structure or
[From
Chivers. T.; Codding,
sm
P. W.; Oakley. R. T. J.
Soc.
Cummun. 1981. 584-lliS.
Reproduced with
permission.!
An even larger number of binary sulfur-nitrogen cations and anions are known.
Reduction of s.N4 (wilh metallic potassium or sodium azide) yields the planar sixmembered ring, S 3N). (rJ8. 16.32a). At first glance one might rhink thai this is anolher
henzene analogUe. An electron coum dispels !hat notion as !here are ren 7T elecrrons
instead of six. Still, lhe HOckel 4n + 2 rule is obeyed and the system satisfies the
requirement for aromaricity. However. four of the 7T eleclrons occupy antibonding
orbitills, which has the effect of wc:tkening the S-N bond !Fig. 16.32bl.
Sulfur-nilrogen compounds often have unprediclable slructures. One example is
the sulfur diimide. PhSN=S=NSPh. for which the following three configurations
could be envisioned:
's s . . . .
I
N
(a)
's
I
N
's . . . .
(b)
Configurarion (a) is preferred rather than the more open slructures (b) and Cc). This
runs counter to our intuition that the most hindered slructure would be leas! stable.
The separnrion between the end sulfur aroms is only 329 pm. compared with the van
lings
779
Fig. 16.32 (a) Structure of
s,N \ ond lbl qualirative
muleculor orbital diaGr.lm.

(From Chivers, T.; Oakley.
R. T . Tnp. C11rr. Clttm.
198Z. /(12, 117. Reproduced

with permission.]
der Waals sum of 360 pm. sugges1ins sij;nific:anl sulfur-sulfur inlernclion. In fac1 one
can wri1e resonance stnJc:tures such as:
R
's-s
I
's,..
which misht lead us to t>elieve that a rins slruc:ture
a beller description. However,
ab initio sclr.consistem field cakuloltions

not support Ihe ring
bul rather
reveal lhal the unusual conformation is the resull of electronic inlor:.clions belween
nitrosen
lone pairs."''
Reduction of 1e1rasulfur tetranitrwe wilh linllll chlori.!c prOOlk:es tel.rasulfur
S4(NHI4 , isoelectronic with sulfur. S,.. Like sulfur. the tetraimide also
exists in a crown
AsS
NH ure isoelcctronic. il has been possible to
p.Wucc a series of ring
,. thai includes ull possible isomers
except those with N-N bonds.
Nol only can S4 N4 be reduced us illusrrnled in lhe
CXllmple. but it can
abo be oxidi:ud. When it is subjcclcd to chlorine. lrilhiazyl lrichloride is produced:
JS4 N 4
+ 602
4N>S 3CI 3
116.591
This cnmr<>und m;oy he convened imo the O:llrrc,pumling lluoridc r

sJJifanuryl chloride:
lo
Cl
,..s,
II
Cl
( 16.60)
,..s, ,.,.s . . . .
N
Cl
&rri>tcr. R. M.: Rzcpa. H. S. J.
.... 0,/ttHt Trmu. 19119. 1Nl9-M>tt.
780
16 1ftorgaftic Chains, Rings, Cages, and Cluste n
Cl
,...s,
II
(16.61)
,...s,N""'s'CJ
Cl
When we consider that complexes with chelating ligands (see Chapters II and 12)
are compounds with rings, we realize that rings with metal a toms are quite common.
In a..ldition to these, however. new classes of compounds nrc appearing regularly in
which metal atoms have replaced nonmetal atoms of traditional nonmetallic heterocycles. Replacing a PPh2 group of a trim eric cyclopllosphazene wit h Cl)W yields planar
(CI) WN ){ PPhzhl and replacing two PPh 1 groups of a tetrameric cyclophosphazene
with VQ2 gives planar (CI1 VN 2 PPh1 h.ll2
lsolobal relationships between metal and nonmetal fragments will undoubtedly continue to be exploited and intense activity can be expected in this area for some time to
come.
Homo cyclic
lnorgonic Systems
Several elements form hornocyclic rings. Rhombic sulfur. the thermodynamical ly

stable form at room tempera.ture. consists of
rinas in the crown conformation.
Unstable modifications,
are known which include n 6 through 11 .. 36. In fact,
sulfur has more allotropes than any other clement.9) Selenium also forms five-. six-.
seven-, and eight-membered rings. but they arc unstable with respect to the chain
form.
Organometallic chemistry has become an important player in the rings of !llllfur. w
The existence of an isolobal re.lationship between S and C p1Ti lends to the prediction
that it should be possible to substitute the latter for the former in sulfu r rings. The
formal replacement of one !llllfur atom in S 6
Ti gives CpifiS5 (or replacing two
sulfur atoms in S. by two CPlTi units gives I
In practice one takes these
"'Wiu. M. ; Roeslcy, H. W.; Nolt<meyer, M: Sheldrlc.k , 0 . M. AtoJ1tw. Clwtn./ttl. EJ. EnJ!/. t9tl. l7,
8.5G-l!SI , and
lhc:rein.
9J SJeUdd. R. Top. Cu". Ctum. tftl, /01, 149. Steudct. R.; SteidoL J.; S:wlow. T. Z. Nutu,fonclo ..
8 : lomxg. CMm., Orr ChLm. 1986, 4/,958-910. Frinl.sconl:linin&bolh sulfurllld scleni&Jm.scc
Steudel. R.; Papa\laSSiiou, M.;
E.M.: Laitinen. R. Anfn>. Clwm. /tot. Ed. Enlll. t!J16, 25,
99-tOI.
.,.
M.; Rauthfuu. T. 8 . AnJI<'w. Chtm. lnl. Ed.
1915. 24, U2-7S7.
Rinv
reactions in the reverse direction. For example,
s,.. may be prepared from the rea.Jily uvailable
781
which is unstable with respect to

TiS5 complex.
(16.62)
I s's/f
cp Ti/
2
'sf
+SCI.-
's/f
s / 5 's f
+Cp.TiCI 2
(16.63)
The
anion that forms in the first step is one of several polysullides
sr. si-.
s!-l. al l of which have open chain structures . The versatility of CJ>:T.S5 as a precursor to other rings and suii\Jr-carbon compounds is shown in Fig. 16.33.
Oxidation of several nonmetals in strongly acidic systems produces polyatomic
cationic species of the general type
Among those characleri7..ed areS!+. Sci+,
v:."
Fig. 16.33 Reaclio"" or Cp,TiS,. (From 0.-.pqjac:. M.: Rauchruss, T. B. ltnKrw Chrm. Int.
EJ. Engl. 1985. 24, 742-7$7. Reproduced wiah permission. I
" &rfonl. N.; P:>ssmore. J.: S:lnden, J. C. P. In Ftum J\tonuto l'olymrr>: 1-'rctronlc Jlnu}DRks;
Utbtno<l. J. F.; GrttriberJ. A.. Eds.: VCH: New Yort, l9H9; Chapat1' 2. Collills. M. J.;
R. J.; SaW)'et, J. F. 1110<11. Clrc-m. 1911,16, 1476-141. Gittape. R. J. Chrm. Sot:.
Jts-Jn.
782
16 Inorganic Chains, Rings, Cages, and Clusters
Sei.i.
Si;. and
ions have been shown to be square planar.
s-s
Jl
[ YaY],.
1+
Se- Se
The structures of s;+, Se!+. and Te;
Te - Te
Note that these are isoelectronic with the previously mentioned

All three are
though1 to be stabili1.ed lo a certain extent by a Hiickel sextet of., electrons.
Many cyclopolyphosphines are known. 'HI The simpler ones, (RP)n (n ,. 3-6) (Fig.
16.34). are prepared by pyrolysis or elimination reactions.
RPCl 2
+ RHP-PHR
--+
!! RPCl 2 +!! RPH1

2
(RPh + 2H0
(16.64)
(RP). + nHO
(16.65)
In addition to the + 3 oxKtalion stale seen in the hornocyclic rings discussed

above. pho:spborus rings exist in which the + .S oxidation stale is exhibited:
The anion or this acid resu lts from the oxidation of red phosphorus with hypohalites in
lllkalinc solution:
(16.66)
Fig. 16.34 SlniCIUres of

(RPI. (n 3-6) molccutes.
R
1Rf'4
.,. Woolins. J . 0 . Non-Mnal Hlnl(s.
011J Clntus; .k>hn Wiley: New Yk. 1\II!K.
783
Rings
There is a series of analogous cyclic thiophosphoric acids with the formula

that may be pt"epared by the oxidation of red or while phosphorus with
polysulfides under a variety of conditions. For e xample, the reaclion of while phosphorus with a mixture of sulfur and hydrogen sulfide dissolved in triethylamine (which
acts as a base) and chloroform opens the phosphorus cage to form the tetr.nnenc
cyclic anion:
(16.67)
The square structure of ahe anion has been confirmed by X-ray

A series of cyclopolyarsines is known. They may be prefl'lred by a generally
useful reaclion lhal is reminiscenl of the Wurlz reac1ion of
chemistry:
(16.68)
Although four- and five-membered rings can be made in this way, I he three-membered
ring requires a speci:l.l, though related, reaclion :
rBu
+ (t-Bu)AsCI 1
(t-Bu)As-As(r-Bu)
1-Bu
As-As
+ 2KCI
(16.69)
1-Bu
This compound is stable only at - 311 "C in 1hc dark and in the absence of air. It
spontaneously igni1cs on exposure to
Alkali metal pentaphosphacyclopcnt:.ulienides (Li and Na) have been obtained in
solution from reactions of retl phosphorus anti dihydrosenphosphide in dimethylformamide:w
P- P
/0'
P
/
P, + tPH,J- - P
(16.70)
Similariay 10 the C,H; anion apparenl if you allow cuch pll\lsphorus a lone p-..Ur of
eleclrons. whic;h
five p orbilals (wilh six electrons) available for rr bonding.
Tmnsition me1al complexes containin; P, rinr;s. however. were known prior to 1he
synthesis of the free P.S ligand (sec: Chupter ISt. U'
arc
97
Falius, H.: Kr..,..,. W.: Shcldridt. W. S . AIINt
.. Baulllcr. M.; Elzbach. T. Corm. IJH. 19'11 .
.,. Baudlcr. M.: AkpapcJIIou. S.; Ouzounis. D.:

MOnsler. H. " " - Chtrn. /ltl. J. Elllfl. 1988. !7.
Angtw. Chnn. 1111. J. Ellgl. 1989.111. 48S.
-
Baudler. M. : Ellllaeh. T.
/111.
J. fjoc/. 1\1111 . !11. 103-104.
1159-1160.
Cht1t1. l11t. Ed.
F.: Meini(lkc. B.; Bullzikiewicz. H.:

Humillon. T. P.; Schodcr. H. F. lll
1991. JO. SIIO-.SS2.
784
16 1norgonic Chains, Rings, Cages, and Clusten
P5)].
and
A triple decker, with
an As5 ring, can be made from pentamethylcyclopenl;wrsine: 1113
CpMo(As),MoCp
(16.71)
1llere is an interesting series of oxocarbon unions of general formula [(C0).] 2 - - (F.g. 16.35). The croconate ion,
was the flrst member of the series to be
synthesized. From a historical poinl of view it is especially intere.sting: (I) It was
isolated in 1825 by Gmelin and thus shares wilh benzene (isolated from coal lar by
Faraday the same year) the honor of being lhe first aromatic compound discovered. (2)
It was the first "inorganic" substance discovered lhat is ar omatic, although its
importance was unrealized until later. (3) It is a baclerial metabolic product and was
possibly the firsl "organic" compound synthesized, predating Wtlhler's synthesis of
urea by three years, although here too the significance was unappreciated at lhe time.
All of 1hese oxocarbon anions are aromatic according 10 simple molecular orbital
calculalions. The arornutic stabiliz:uion of the anion is apparently responsible for the
fact that squaric acid (H 2C.04 ) is about as strong as sulfuric acid.o< There is a
considerable and growing body of knowledge of the chemistry of these systems. but
most of it is probably more appropriaJe to a discussion of organic chemistry. as
In a formal sense, silicon might be expected 10 parallel the extensive alicyclic and
aromatic chemistry of carbon, and to some extent it does. SubsliiUiion of hydrogen
aJoms by methyl groups seems to stabilize these systems. A large series of pcrmethylcyclosilancs can be synthesized by treatment of chlorosilancs with an active
metal over a prolonged period of lime:
c,o;-.
+ Na/K
f,;k (Me2Si)x +
(b)
(16.72)
(Ct
Fig. 16.35 Cyclic oxoc:ubon onions: (a) squarnre: (b) croeonure: (cl rhodizona1e.
"''Scherer, 0 . J.; BrOck, T . Anttw.
Int. Ed. Elftl. tm, 16. S9.
J.: Schwalb, J.: WolmenhluKr, 0 .: Kaim. W. : Gross. R.

Chm. Int. Ed.
&tl. 1916. 25, 36)-364. O.mizo. J. A.: Rult-Maz6n. M.: S:>lcedo, R. ; Toscano, R. A.
1u: Scherer. 0 .
Ch<m. 1990. 29. 879-UO.

Rhci<llliOW. A. L.: Foley. M. J.; Sullivan. P. J. J. Am.
S<x-. 19111, 104, ml-4729. Sec abo
OiM:rio, A.J. : Rheinaold. A. L.
Clttm. 1990. 29. 798-804.
""
11131 oxolic :lcid conl:lini,. catbon in a
oxidouion SIDle: buJ not arOINilic has a K 1
eQUIIIO Kz lOr sqU:Jric and sulfuric acids. and Kz ror oxalic acid is Jhrcc: orders cl
m;aani1ude smo.er. Fora difference: o(opinion conccmifla lhc:
ell he oxoaubon anions.
sec: Aih.:tn. J. J. Am. Cit.,. S<>c-. t98t. /OJ. 16JJ-16JS.
lOIS Oxocarbons; Ww. R. , Ed.; Aadenoic: New Yotlc. 19110. Sciu. Q. ;
P. Ottn. Rn. 1992.
91. 1227-!160.
Ml)
a,,,.
- ----'2- ---
Coges
78 5
T he product consists of vurious amounts of high pQiymer r.r is very large) and discrete
c yclosilanes with n "' S-l S. This is the largest homulogous series of cyclic compounds
now known except for the cycloalkanes. Although these compounds are formally
saturated . they behave in some ways as aromatic hydrocartxms. They can be reduced
to anion radicals. and EPR spectra indicate that the unpaired electron is d clucalized
over the entire ring. I06
Cages
Cage struc wres range from clathrate compounds on the one hand to me1al-metal
clusters a nd boranes on the o1her. These classes are discussed elsewhe re ,1117 and this
sec 1ion will be restricted to certllin
compounds having cage strucwres.
The simplestcagelype molecule is white phosphoru.s , P . Although P2 molecules,
isoelectronic with N:. are found in phosphorus vapor at higher temperatures. P4 is
more stable at room temperature. Ins This molecule is a tetrahedron of phosphorus
atoms:
Such a Slructure requires bond angles of 6C'/'. Inasmuch as the smallest inh:rorbi1al
angle available using only s and p orbital$ is 90" (pure p orbitals). the smaller bond
angle in
must be accomplished either through the introduc tion of d character or
through the use of bent bonds. Ab initio calcula1ions show the importance of J orbital
participalion. I09 In spite of ring strain. the P. molecule is stable relative to P: or the
nonexistent PH. Never1heless. the molecule is quite reactive. It can be stored under
water . but it reacts readily with oxygen to form P.010 of1en called phosphorus
penloxide. based on the empirical formula, P!O,:
(16.73)
Other phosphorus oxides P.o. P40 7 P.o

are known b ut nul casil) prepare.!. t to> For example. P4 0,,. a liquid at room
(mp 23
can b.: ob1aincd
by controllc.J oxitlation of
fo llowed by .Jislilhuion: ll t
(16.74)
This molecule m (T4 symme1ry) has four lone pairs of electrons (one for each phosphorus) which can be donated to one, two. three. or four oxygen atoms to form other
- Wcsl. R. P11u Appl. Ot,. 19112.J4. lQ.It- t0$0. BrousJ>. L. F. ;
R. J. Am. Chm. S.l<'. 198t.
/OJ. J049-JQS6.
""Oalhrate compounds an
bolh In Oapler II nil eatlic:r in lhis ehapcr. while mcJal
dw!ten nnd bomnes are rounoJ l:lter in lhis cllu.pler
.. Bock. H.; Mliller. H. f ttorx. Cit,. 198-I.ZJ. 4l6S-436S.
""Schmidl. M. W.; (;ardon. M. S. 1-11 a,..,, tt&S,H. 4$0}-4$06.
t to AI cun:nl prices you can buy P.010 ror So.tO/a. Wllile P40 6 eos1s :!bout S2Xl/S.
Ill Heirrze. D. Pa.u App/. Chnn. 1975, 44, 141-172.
Ill Jans..,. M.: Moebs. M. l lfOI'I.
1984.1J, 4486-4488.
786
16 lnotgonic Chains, Rings, Cages, oncl Clus ters
160
0
I_)o..__ l
_)o "-16-l pl
168 1
' ,.,,
P' ,.... P..._ / P

0
0
(141
&14S
6-...__o
l160
p
"-p
' , . , , /.0::,0
0
0
(C)
(b)
Fig. 16.36 Phosphorus

CllF molecules: tal
Cbl P40,: (c)
(d)
P.O.: (e) P.o..,. [Data
P.o.:
(disuonc:es in pm) taken

from Jansen. M.: Moebs.
M. l n<lf/1. Chtnr. 1984. ZJ.
with permission.!
(d)
oxide cages (Fig. 16 .36). All are anyhydrides that react readily with water to form 1he
com:sponding acids:
P4 0
+ 6H 20 -
4H 2PHO;,
(16.75)
P40 1a
+ 6H 20 -
4HlP04
(16.76)
Tile P4 0, molt(:ule reacts to fonn both phosphoric acid and phosphorous acid. In
addition to the discrete cage molecule pictured in Fig. 16.l6e. phosphorus pentoxide
also exists in several polymeric fonns.m
White phosphorus can be converted readily to its more stable allot ropes:
(16.77)
.. .,.:;:::,.. P.-
(block
(16.71!)
Crystalline black phosphorus has u corrugatet.llayer structure.

.. Red phosphoru.s" does not appear to be a well-defined substance but differs
according to the method of preparation. It probably consists of random ch<tin:;. The
r.th:: of formation is increased by certain substances
as iodine which appear to be
incorporated into the product.
The chemistry of phosphorus and sulfur is considerably more complicated than
phosphorus-oxygen chemistry.m Only two phosphorus
P..S 10 and P4 S 9 , are
isoelt(:tronic and isostructural with phosphorus oxides. The former may be prepared
and sulfur to react:
by allowing stoichiometnc amounts of
Sh;armo. 8. 0 . tnurr. C.Vnr. 1911,16. 4S4-4SS.

,,. fCf" this
Oilier itlkres&q dem<N:II
EWfiU'IIls; Wiley: New Yort. 19R
Ill
"' HolT,_, H .: 8ccJ<e..Guehrina. M. Tup.
s OonoJhlc:. J . Tlrt St,mms

C/rn. 1976.11. 193-171.
Cages
4P4
+ SSw -
4P.S10
(16.791
By mixing phosphorus and sulfur in appropriate stoichiometric quantities.

P4 S, may be obtoined. Slow oxidation of P4 S 3 with sulfur yields
4P4S 3 + S 6
4P4Ss
--
787
and
(16.80)
Two cage phosphorus sulfides may be synthesized by the formation of sulfide bridges
through the action of biS(trimethyltinl sulfide.II6
l
(Me1Sn).S +
'P.....- \'s
p
P/\'S
s....._/.....-P
S....._ t_:)P
l's.s I
(16.81)
'
(a-P4 S1l:l
s.....-\'s
I s I
P....._ /.....-P
p
1/
(16.82)
' I
The s1ructures of all of these sulfides are known (Fig. 16.37). They are all derived from
a tetrahwron of phosphorus atoms with sulfur atoms bridging along various edges. All
exccpl P4 S 10 and P4 S., retain one or more P- P bonds.
The heavier congeners of phosphorus resemble it in a tendency to form cages.
Both arsenic and antimony form unstable 1etrameric molecules which readily revento
polymeric structure. . Cage molecules as well as polymeric forms are also known for
As4 0,. and Sb4 0,.. In addition there are a number of sulfides, some of which are known
to .:xist as c:g.:s 1Fig. !t..3K).
By extension of the renctions involved in the formation of cychlpl>lysi!anes. West
am! Carh<:rryll 7 synt hesized bicydic "nd
perm.:thy!polysilan.:s such as:
Me
.....-Si....._
Me,Si .1\,.SiMe,
e,.,,, .
Me,Si
Me];
7 SiMe,
'-Si.....-
Me
"Griffin. A. M.: MinshAll. P. C.:

G. M. J . Cftmt. $<..:. Cl"'"' Cmmum. 1976.809-810.
111 W<Y.. R. ; Carbc:rry. E. Scitncr 1975. 189. 179-186.
788
16lnorgonic Choins, Rings, Coges, ond Clusters
f"og. 16.37 Molecular

SlruciUres c:J some
phosphorus sulfides.
Distances in
Fig. 16.38 Molecubr

Slructures of two arsenic
llllfides. Distances in
l)icome1ers.
In order to get branching to form cages (bridgehead silicon atoms) some methyll richtorosilane is added to the dimethyldichlorosilane in the reaction.
In the limited space allowed here. it has been possible to mention only a few of the
many nonmetallic inorganic cages. If we consider those which also include carbon
atoms, we have an even larger group from which to choose. One of the more
remarkable cages to be synthesized recently is (I-BuCP)4 which has a cubane structure. us Two molecules of trrt-butylphosphaacetylene (I) undergo a head-to-tail dimerization to give an intennediate (2) which is thought to dimerixe once a,gain or react
" " Wetdinc. T.; Schneicb, J.;

1989.18. IOt}-1014.
w.-. 0 . : Kric1er, C. G.; RcJiU, M.
O t- . /111. U . En,t.
Boron Coge Compouflds
789
with two additional molecules of the Slllr1ing material to give 13) which 7Jps up' ' to
give the final product 14).
P='C--f(ll
(16.83)
())
Boron Cage
Compounds
Boranes
(41
Reduction ofboroo halides might be expectell to produce boranc. BHl. Ho-ver. it is

impossible to isolate the monomer. oil syntheses resulting in diboranc:.
. ....
+ 6NaH---+ 6NaBF4 + B1 H 6
+ 11 ---+ B1 H6 + 2Naf + H 1
2KBH 4 + 2H 3 P04 ---+ B1 H6 + 2KH 2 P0 4 + 2H 1
8BF3
2NaBii.
(16.84)
(16.85)
(16.86)
Although BH, exists in 1hc form of Lewis acioJ-b:osc ooJoJucts anoJ as a presumable
imermeoJiatc re."lCtions of o.lihomn.:. only trace
uf the fn:e mol.:culc have
been o.lctectco.l. llle equilibrium constant for <.limeri7.alion is upproxim:ucly
the
enthalpy of dissociation of the dimcr to the monomer is about +ISO kJ mol- 1 or
slightly more.JlO
(16.87)
Oibordne is the simplest of the boron hydrides. a class of compounds that have
become known as tltctrtm dt'/icit!nl. They are electron deficient only in a formal
sense-there are fewer electrons than required for all of the adjacent atoms to be held
together by electron-pair covalent bonds. The compounds. in fact. are good reducing
Fur a discussion o( Jhe synJhtJic: chcmisJry al 8 - H compounds. sec Short, S. G. In

Cllut.n. tJJHl Polyrrrtrs t1{tltt Muin Grwp /rMmts; Cowley, A. H .. Ed.; ACS Symposium Sctid
232. American 0cmica1 Socidy: W...hincJon, DC,
o:o TrimcJhylboroa. unlike BH1 shows no Jtndeney 10 dlmerize.
790
16 ln019onie Choins, Ri"'9t, Coges, ond 0111ters
agents and show no tendency to accept electrons when offered by reducing agents. A
number of approaches have been U$ed to rationalite the bonding in these compounds.
The most successful and extensive work in this area. as we shall see. has been that of
William N . Lipscomb. Ill Before proceetling with an examination of the bonding in
diborane, it will be helpful to examine its structure
16.39). Each boron atom is
surrounded by an awroximate tetrahedron of hydrogen atoms. The bridl?ing hydrogen
atoms are somewhat further from the boron atom and form a smaller H-B-H bond
angle than that for the terminal hydrogen atoms.
The earliest attempt a t rationalizing the dimerization ofborane invoked resonance
in a valence bond (VB) context:
'B-:::
./ '
H. /
'
(16.88)
Although adequate from a formal point of view. it suffers from the usual unwieldiness
of VB terminolOgy when extensive delocalization exists. A second auempt considers
the B1 H!- anion as isoelectronic and isostruaural with ethylene, c;H. Such an ion
would have a cloud of electron density above and below the B-H plane.m The
neutral
molecule could then be formal ly produced by embedding a proton in the
electronic cloud above and below the plane of the B2 H!- ion. Although this may
appear to be somewhat farfetched. it is but a simplistic way of describing the bonding
model which is currently accepted as best- the three-center. two-electron bond.
fig. 16.39
SINCIUre or
B:H.,
o:o Prorc:ssor Lipscomb's work h;a. been or such vatue lh:U he rccci..:d the 1976 Nohd Prize in
chemistry (see Scwnt:r 1m. 19d. 11147- lOSS
his Nobel Llwc'c:lle a<ldrcs.s). II has bccll aptly
<11id, "Boron hydOOc. Dr< the children or 1M century, yet ll>e discovery or polyhe<hl bor:Jn&:.s.
c:uboroiRCS, IIIICI me1alobot:anes und lhc subsequc:nl cloborolion or chcmislry. Slruclun:. and
1hcory. and 1hc incmlibly npid one consi.krina lhc IINIIl number or
ore urnon& 1hc
""'jor dcvdopncnts in inoiJIInic chcmisuy" IB,un Hydridr Clor,.,utry: Mucucnics, E. L . Ed.;
Ac:>domic: New York. 1915).
r.,..
I!!
NOCc th3l tbs is IIUC whclbcr lhc .,_.,model a bcftlboocl modd is employed ror lhC dcutlk
bond.
Baron Cage Co,pounda
791
Consider each boron atom to be spl hybridized. D The two terminal B-H bonds
on each boron atom presumably are simple u bonds involving a pair of electrons each.
This accounts for eight of the total of twelve electrons available for bonding. Each of
the bridging B-H-B linkage.s then involves a deloculi7.ed or three-center bond as
follows. The appropriate combinations of the three orbital wave functions. 4>0 ,. 4>6 ,
(approximately sp-' hybrids), and <PH (an s orbital) result in three molecular orbitals:
t/lh
= l<J>o, + !4>o, +
-
{16.89)
= l<Pu,
(16.91)
(16.90)
"' a
t/1.,
!<J>e, +
where t/1, is a bonding MO. t/1., is an antibonding MO. and 1/Jn is. to u first uwroximation. a nonbonding
The diagrammatic possibilities of ovcrtap toge1her with
sketches of the resull.ing MOs and their relative energies are g.iven in Fig. 16.-40.
Each bridging bond thus consists of a bonding MO containifl! two elec1rons.
Ahhough 1he nonbonding orbital could conceivably accept an additional pair of
electrons, this would not serve to stabili:te 1he molecule beyond that achieved b!' the
configuration #,.The second B-H- B bridge likewise may be considered to have a
configuration .Y,. This accounts for the total of twelve bonding electrons and provides
the rationale for the existence of the dirner (fig. 16.41).
Oiborane provides examples of two types of bonds found in higher bontnes: the
two-center. two-electron B-H termil131 bond und the three-center. two-electron.
ng.
16.40 Qualilalive descril"ion of aJOmi.: orilhal fld'll. resulting

molecular
energy level di:larum I<.en let I fOf' one B-H-B bc-idge
otbiu.ls IriShII. and I he
in dibor.lne.
I::J 1bis isCftly
(-
ProNc:m 1"-lll. The1>1Jume hc doco; naJIUI upon the
rllllure of lhe hybridiullioc>.
I!A 'The exacl enei'JY of IM Ofbilal v:ari<s

on lhe !Qiutc of Ihe bonclin&
of lhe
:uoms invdved For our Pllf'IIC*S il cllles no horm land simllli/ie$ lhc modc:ll il iJ io nssurncd 10 be
nonbondilll.
792
16 Jnorgonic O.oins, Rings, Cages, ond Clusters
,.,
(b)
Fig. 16.41 (a) Qunlitalive piclure of bonding in dibomne. (b) A common method of
depicling 8 - H- B bridges.
bridging B- H- 8 bond. Two other bonds are of imponance in the higher analolliJes:
(I) lhe lwo-center. two-electron B-8 bond. best exemplified by the boron subhalides. X!8-8X2 ; and (2) the three-center, tw().electron 8-B-B bond , which
may be formed by overlap of three o rbitals from three corners of an equilaterallriangle
of boron atoms (Fig. 16.42).125 Like the three-center 8-H-8 bond. three molecular
orbitals will result. of which only the lowest energy or bonding one will be occupied by
a pair of electrons.
With lhis repertoire of bonding possibilities at our disposal, we can construct the
molecular slructures of various boron-hydrogen compounds, both neutral species and
anions. The simplest is the tetrahydroboratel26 or borohydride ion, BH4. Although
borane is unstable wirh respect to dimerization, the addition of a Lewis base, H-.
sruislies the fourth valency of boron and provides a stable e01i1y. Or her Lewis bases
can coordinate as well.
B2H 6 + 2NaH
2Na8H 4
(16.92)
8 : H,. + 2CO
---+
2H3 8CO
(16.93)
8 2H6 + 2R3 N
---+
2H 3 BNR3
(16.94)
0 --<
--oa
.
+
8
(a)
\:)
Fig. 16.42 The closed lhree..:cnter. two-eleclron 8-B- 8 bond:

boron atomic orbilals; (b) simplified repre.enlation.
tbl
formalion from lhree
'" For some heJcrOaJOm sysJema an open or linear 8-8-8 bond which more resembles Ihe open
8-H- 8 bond discussed above is required.
r. Telrahyck"oborole i$ the preferred name.
loran Coge Compounds
793
Allhough the ammonia adduct of BH3 is stable, it must be prepared by a method that
does not involve B2 H6 such as:
(16.95)
Direct reaction of ammonia and diborane results in the "ammoniate" of diborane,

which has been shown to be ionic . m
B1 H6 + 2NH 3
(BH1(NH3)z] + + BH;
(16.96)
This unsymmetric cleavage:
is typical of reactions with small, hard Lewis bases and funher examples will be
discussed below. Larger bases. such as phosphines, promore symmetric cleavage:
Diborane is very air sensitive, reactinc explosively when exposed to air. Although
it is said that in extremely pure form, the compound is stable in air at room temperature. the!SC conditions are rurely met. In general. the higher molecular weight
bornnes are much less reactive. For example, decaborane (8 10H 1J is quite stable in
air.
All of the compounds discussed thus far (except diborane and decaboranel contain only two-center. two-electron bonds. A simple boron hydride containing three
types of bonds is terraborane, B4 H 10 (Fig. 16.43). It is formed by the slow decomposition of diborane:
(16.97)
In addition to terminal and bridging B- H bonds. this compound contains a direct

B-B bond. Terraborane undergoes both symmetric and unsymmetric cleavage CFIC.
16.44). l.aq,'er Lewis bases tend to split off 8H 3 moieties, whil:h are cithcrcomplexed
or allowed 10 dimcrize to form .Siboranc :
B4 H 10 + 2Me 3N Me3NB 3H7 + Me1 NBH 1

2B4 H10 + 2Et1 0 ----+ 2El1 0B,H 7 + B1 H6
2B 4 H 10 + 2MezS -
(16.98)
(16.99)
2Me1SB 3 H, + B1 H,
(16.100)
Small, hard Lewis bases such as ammonia und the hydroxide ion result in unsymrnetric cleavage, ie., the splitting off of the BH"i moiety:
B4 H 10 + 2NH 3
---+
(H 2B(NH1h]+ + (B1 H_)_
2B4 H 1o + 40H----+ (B(OH)J-
+ (BH4r +
m Funbcr bealinc pves boruine csee Eq. 16.3-41.
2(B3 H1
(16.101)
(16.102)
794
16 1no rgonic Chains, lings, Cages, and Clusters
Fig. 16.43 Bondi,. and structure ol letr:lbonne. B.H,., (From Mueuenies, E. L. TM

Clwmistry <I{ Borott 011d Its
Wiley: New York, 1967. Reproduced wilh
permission .I
I H
;r- 81"
H /
H,
B I
_..H
'
(a) ad unsymmelric
(bl cleaYll&e or tetr:lborane.
v
t H
8
_/'H
Fig. 16.44 Symmetric
H
I
IL'
/H
'H
tal
(b)
The reaction in Eq. 16. 102 can be considered os 8 n obstroction of BH; if it is assumed
that
forms and disproportionates:
(16.103)
Rather than continue to progreu from less complex to more compl.:.x

boron-hydrogen compounds. il will be more convenienl lo jump 10 a complex but
It muy be synlhesi"cc.l by the
highly symmetric borohydride ion .
of the (BJH,r ion:
S(B3 H 8 )
- + (B 12 H12]2-
+ 3(BH.r + 8H1
(16.104)
It is not necessary to use [BJHJ- directly in this reaction; it may instead be formec.l in
situ from c.liborone and borohydride:
(16.105)
1
The [B 12 H 12] - ion is a regular icosahedron of aloms. each of the twenty faces
being an equilateral triangle
16.4Sa). All of the hydrogen atoms are external to
the boron icosahedron and are anached by terminal B- H bonds. The icosahedron
itself involves a resonance hybrid of se.eral canonical forms of the type shown in F.g.
16.4Sb and c . Both two-electron, two-cen1cr 8-B and two-electron, three-center
B-B-B
are involved .
An icosahedral framework of boron atoms is of considerable importance in boron
chemistry. Three forms of elemental boron as well as several nonmetal boridcs
Boron Coge Co,.pounds
'"'
795
fbi
16.45 Cal
structure o( 1h.: IB1: Ho:f- anioo: lbl . ICI rron1"'"'back ur 1he
[B,:Huf- framcworl< showina one or many t:tnonical f\lrmS
10 Ihe reson:tnct
hybrid. [Cal From Murllenies. E. L.
Chtmlstry of
tmJ fts Ct>mpounds: Wiley:
NtmMetuf<: l'renlict H'III:
New York t%7: 1bJ rrom Jolly. W. L. Tlw C/l.,ti.u ry
Englewood Cti!Ts. NJ. t%6. Reproduced with
/1,,,,,.
conmin discrete 8 12 iclll\Othet.lr:o. Fur example . nrtlomhohct.lr:tl bontn c:tm,ish of

layers of i.:t"ah.:dra linked wi1hin .::tch layer by lhrcccCnlcr a- B-a btmth ami
between layers by 8-B bontls !Fie. tft.4ftl. P.Ritombvhcdr"l
ttftwclve
icosahctlra
abouc a ccn1r.ll 8 1: uni1. i.e . B 12rB 1:1 12
boron consists oficosahedr.t linketl. not o nly by B- B bonds b.:1ween the
icosahedm themselves. but also by
coordination 10 single boron
Sevcr.tl boranes may be considered us fragments o f n 8 12 icosahct.lron lor of 1he
[B 12Hd 2- ion) in which extra hydrogen atoms are used to ..sew up .. the u nused
valences around the edge of the fragment . For example.
14)1!M (rlg.
16.47a) may be considered a B1:H 1: fr.tmework from which a, and a,. (Fig. t6.4Sl
have been removed leaving ..dangling.. lhrcc-centcr
that u rc completed with
hydrogen atoms to form B-H-B bridges.
Other
of bornnes thai are ico!lahetl r.tl froJGI!lents arc !t.:xilboraner 101.
which is a penlugonal prism (Fig. 16.47bl.
I I l. similar to the former ..-ith
or
""The prcU Gives lhr - boron ...m. iln.lllw tlltml>:r ... p:orcmhcso. pvcs llw nufl1bcr cl
ltydrop:n 111om.. Thus tlccnbor;tft<;l l41 IS 8 .,H
7'16
161nargonic Chains, Rings, Cages, and Clusters
Mg. 16.46 Structure of a

rhombol>tdrnl boron. The
icosahedrn ure linked within
the layer via lhree-cenler
bonds. This layer is linked
to the layer above by 8 - 8
bonds arisina from the
boron atoms marked and
to the layer helow by three
additional boron atoms nOI
seen on the opposile face.
ng. 16.47 Mola-..lar Slruclures or boranes relaled 10
(a) decaborane{ l 4) formed

by
o( atoms 8 1 and 8,; (bl hexaborane{ 101. No1e 1ha1 t he
pyramid is an
apical fr..gment
an icosahedron. (c) Octaborane( l 21 related 10
by removal of 0 1
8:. 8,. D.,. I From
E. L Tht! Chrmisuy <>[Boron and Its Compoumls; Wiley:
New York. 1967. Reproduced with permission. I
or
(bt
lot
(<I
loron Coge Compounds
797
a basal boron atom missing. octabornnc(l2) (Fig. 16.47c). and nonabomne (IS).
Allhough relating borane structures to icosahwra was the first successful means of
systemutizing the structural chemistry of these cages. further experimental work
revealed that the icosahedron or
was merely I he uwer limil of a series of
regular deltuhedra.2Y [B.H,.]2 -. complete from n = 6 lo n = 12. Ann a 4 structure
also exists in the form of B.Cl 4 (Fig. 16.48). If all of the vertices of I he deltahedron are
occupied. as in lhe (B,.H.12 - series. the structure is called a doso (Gr.. "closed'')
structure. II is possible to correlate lhc structure of a bor.me or its derivatives with the
number of electrons involved in the bonding in lhe framework of the dellahedron.no
The number of vertices in the deltllhedron will be one less I han the number of bonding
pairs in the fr.llllework. This approach is sometimes called the polyhedral skeletal
Fig. 16.48 (U) The structure of the [B.H,j 1- anion comp.1red to an idealized dodecahedron.
[From Guggenbereer. L. J. /mKg. Chem. 1969. 8. 277t. Reproduced wiah pormission.f (b)
Molecular structure of B..CI.. compared to an idealized tetr.shedron. (From Muencrties. E . L.
The Clremistry of Boron and Its Compounds; Wiley: New York. t%7. Reproduced with
permission. I
'"' A dcltahedron is a polyhedron with nil faces Ihat are equllalcnll uungles. The dell2hcllr from n a
4 ton a 12 ore
(41. trisonnl bipyrnmid tSl. oclohcdrcln 161. pcnangonol bipyramid (7).
b;sdisphenoicl (cloclccllhedronl (81. aricappcd trisonnl prism t9). bicappcd square onlipri!m ItO).
octadcalhedron (II). and
(12). Mos1 of lhese ore illu.ar.tled in Chapters 6 and 11. Sec
also Fi&. 16.$0.
IJO O'Neill. M. E.: Wade. K . In
lnttructl11ns "'itlt &mm Cltuun; Grimes. R.N .. Ed.: l'lcnum:
New Yool<. 1983. Wade. K. AJr. lnorJI. Clm.
1976, 111. 1..()6. Rudolph, R. W. Ace.
Ctttm. Rrs. 1976.9,446-452. Grimes. R.N. CumJ. Cll<'m. R<"' 1979, Z/1, 47-%. O'Neill, M. E.;
OrJianom<tulli<Wilkinson. G. ; Slone. F. G. A.; Abel, E.,
Wade, K. In
Eds.; Pcrsamon: New York. 191!2: Vel I. Chapa..- I.
798
16 Inorganic Chains, Rings, Cog.., one! Clusters
electron pair theory or more often Wadt' 's rufrs. For the cfuso series, the number of
framework electrons equals 2n + 2. To count fra mework electrons in, for example.
one notes that each boron atom has one o( its three valence electrons tied
u p with the rxo 8 - H bond (an exo B-H bond is one extending radially outward
from the center of the cluster; see Figs. 16.4S und 16.48) and it thus has two to
contribute to the framework, giving a total of 2n (in this case 24) electrons from the B
atoms. No neutral 8,Hn species are known , but we have seen an array of dianions
corresponding to the 2n + 2 rule. The 26 electrons in (8 t 2H 1,] 2 - are just the number
required to fin an of the bonding molecular orbitals in [812 H t!p- and correspond to 13
{tr + I, n z 12) electron pairs as expected for an icosahedron.
If we (in a thought experiment) remove a boron atom from " vertex of a cfoso
structure. a cup-like or nest-like structure remains (Fig. 16.49). Such structures are
termed nido (latin, "nest"). We have seen that structures such as this contain extra
hydrogen atoms to "sew up" the loose valencies around the opening. Tile nido
slnlctures obey the framework electron formula 2n + 4. Consider 8, H9 for example.
Five exo 8 - H groups will contribute two e lectrons each and the four "extra"
hydrogen atoms will contribute four electrons fo r a total o( 14 (at + 4. 11 z S). This
corresponds to 7 (n + 2) electron pairs and the geometry will be derived from an
octahedron (n - I vertices). The structure is thus a square pyramid nido form derived
from the closo octahedron. The extra four hydrogen atoms form bridges across the
open edges of the nest {F'J8. 16.49).
If we remove two venex boron atoms, the resulting framework is an arudrno
(Gr., "spider's web") structure. With two vertices missing, the structure is even more
open th:ln is the nido case and the resembbrn<:e to the parent cfosu structure is less
apparent. Arachno slnJctures obey the electronic formula 2n + 6 (or n + 3 electron
pairs). Pentaborane(ll), 8 5 8 11 , must therefore have an
structure. In the
araclrrw series the extra hydrogen atoms form tndo 8- H bonds (lying close to the
frdmework) as wen as bridges.
The hypho (Gr ., " net" ) series of boranes, with electronic formula 2n + 8. has
been suggested to augment the doso. nido, and arttchno series. All hough no neutral
bordOO:S fit this scheme, some borane derivatives do. II is also
10 construct
units consisting of more than one of the above types. These are cal led <mvwrttu
(latin, "joined subunits") structures .
The complete structural relatiomhips among I he ,.,,,su, ,icJ.,. und ttrudtlltl species
represent the
:rrc shown in Fig. 16.SC. The dkconal li nes connectinG 1he
tl
tbl
Fig. 16.49 (al Strucun o( .UJo-pcnr:obor:lncl91: (bl :stn.raure of , ;.u,.dCCOibor.lno:t t41. Cf.
rlosn slrUCJUres ia F'oa. t6.SO.
Boron Coge Compounds
Nido
Ooso
799
Arochno
-+-/.A/ A
.
//!#-
. $ /Ji!l
/
Fig. 16.50 Structurl relmionships o( cla1a. ni<l11. and
lx>rne.,. Structural hoot<lloaucs are conncctcll by the diagonal tines:
lhC1)(ctical retlux reactions arc in horizuntal rows. I Frum Rudolph.
R. W. Ace. Chem.
1976. 9, 446.
with permis:;ion.l
800
16tnorgonic Chains, Rings, Coges, and Ousters
hypothetical transformations discussed above, removal of boron vertices moving from

lower left to upper right.t3t The horizontal series represent structures having the same
number of boron atoms but differing in the IOta! number of framework electrons so as
to conform to the doso (2n + 2), nido (2n + 4), or aradmo (2n + 6) electronic
specifications. In a few cases (see below) the change from one structure to an adjacent
one on the same line can be effected by a simple redox reaction, but in most instances
this is not so. However, we can probably anticipate more examples of this type of
transformation now that the general principles of framework electron count and
structure are beuer understood.
What is the source of the 2n + 2, 2n + 4, and 2n + 6 rules and their correspondence with the cfoso, niJo. and ttrtiCitno structures? Space does not allow derivation of the molecular orbitals for deltahedra, but the results may be stated simply: For
a regular Jeliulri!Jron having n vertices. /here will he n + I IJontfing molecular
orbiwls. The electron capacity of these bonding MOs is therefore 2n + 2. This gives
the highly symmetric closo structure. If there are two more electrons (2n + 4), one
bonding MO and one vertex must be used for these extra electrons rather than fur a
framework atom. and a nido structure with n missing vertex results. Although the
electrons in boranes are delocalized and cannot be assigned to a specific region in a
particular structure, the parallel between the extra electrons in niJo structures and
lone pairs in molecules like NHJ is real . The 2n + 6 formula of arachno structures
simply extends these ideas by one more electron pair and one more vertex.
Carboranes132
Carbon has one more electron than boron. so the C-H moiety is isoelectronic with
the B-H- or BH 2 moieties. Note that an isoelectronic relationship also exists
between C and BH or s-. In a formal sense it should be possible to replace a boron
atom in a borane with a carbon atom (with an increase of one in positive charge) and
retain an isoclectronic system. The best-studied system. C2 Bt0 H 12, is isoelectronic
with [B12 H d 1 - and may be synthesized readily from decaborane and alkynes and
diethyl sulfide as solvent.
B10 Ht 4 +
B10Ht 1 2SEt1 + H 2
+ RClsCR
---+
(16.106)
+ H1
(16.107)
The acetylene may be unsubstiiUted (R a HI or

in whic h case the
reaction p.-oceeds even more readily. The resulling compound is known as 1.2
dicarba-c/o.m-dodecaborane(l2), or the ..ortho" carborane. and is isoelectronic and
It is stable to both heat and air, but it isomerizes at high
isostruciUral with
temperatures to the 1,7 (..meta" or "neo"lsomer) and the 1,12 ("para" isomer) (fig.
16.51 ). The mechanism of isomerization. thought to be intramolecular. has been
discussed for many years.m
Other dicaboranes are derived from the corresponding pentaborane(S). hexaborane(6), hexaborane(8), heptaborane(7). octaborane(8). nonaborane(9), and deca"' Only the exo hydroJ!Cn atoms ace shown in Fig. 16.50. 1lle numhcr orbricJcina and endo hydf01:cn
atom wiU vary dcpendina upon whether the spcciell is neulr.ll or ionic. ha., hetcroatoms (see
below). hos a Lewis base coordinated to it. etc.
m Grimes, R. N. Ado. lnor11.
1983. 16. SS-117. Onok, T . In
011/<tn<>mrtullic
Wilkinson. G.; Stone. F. G. A.; Abel. E. W. Eels.; Pergnmo<1: Oxford.
19lr.!; Vol. I. ChapterS.
tJJ
Johnson. 8. F. G., J.
Soc. Chrm. Commm.
t986. 27-30.
lorOfl Coge Compounds
SOT
6zoc
.50 "C
fig. 16.51 Structures and isomerizttiuns d the three isomers of

dollecaborane. 0 B; e = C.
borane( IO) dianions, IBnHnf- . The monocarboranes. CB, H 7 and CB5 H9 , are also
known.
The carboranes conform to the electronic rules given above for boranes and are
known in closo.
and umr1t11u
When upplying the formulas to the
carboranes, each C- H group should be regardctl us donming thru electrons to the
frameworic count. Some carboranes provide interesting examples of the possible
16.50 mentioned :lbove. For example: J}.l
horizontal transformttions
dost>-<;B,.H11 + 2c- [nitla-C:B9H11f - Metallacarboranes13S
Fig. 16.52 Structure uf the

IC: O..H 11 1:- anion. The
five orbitals direct! towurd
the missins npicul boron
lnc:tu<lcd. [From A<lk:r.
R. G.: Hawthorne, M. F. J.
Am. Clltm. Soc. 197U , 91.
6t74. Reproduced with
permi>sion.l
(16. 108)
[closo-C1 B,.H 11 ) + 2e-
(16. 109)
Strong bases attack 1.2-dicarba-dnso-dodecaborane( 12) with the splilling out of a

boron atom:
C:B111 H 1: + MeO- + 2MeOH __.
+ H: +
(16. 110)
The resull ins uniun is the conjus:llc ba>e of :1 strons acitl whio:h m:y b.: obtained by
adtlification:
(1ft. Ill)
Conversely ,treatment of the anion with the very strong base sooium hytlritle abstracts
a
proton:
IC:B9 Hd - +
lC: B,.H 1 ,11 - + H: + Na
NaH
(16.112)
The structure of the [C1 8 9H 11 ) - anion is shown in Fig. 16.52. E:1ch of the three boron
atoms and the two carbon atoms on the open face of the cnge tlirects an orbital (taken
as spl for convenience) toWllrd lhe apical position occupied formerly by the twelfth
boron atom . Funhermore. these orbitals contain a total of six e lectrons. They thus
"'O>owdllry, V.; Prcttcr, W. R.: lUI. 0 . N.; Ruck>lph. R. W. J. Am. Chl'rrf. Soc-. 197). 9$,
45ii6-4S6.S.
r Mrtollltlt'rurrimu wiJh Bor"" Ostt"<r, Grime.. R. N., Ed.: l'lenum: New Vorl<, tW-o Grimes,
R. N. In Ct""puhr..sir Drl<uNH>Wtltit'
Wilkinson. G.: S1one. F. G. A.: AbeL E.,
Eds.; PcfJ1V11Uft: Oxford. t982. See :>1110 KeMedy, J. 0. Pro11. lnotR. Ch..,. 1986, J4, ltt-434.
802
16 1norgani<: Chains. Rings, Cages, ancl Clusters
beaT a striking resemblance 10 lhe p orbilals in lhe 1r syslem of cyclopenladienide

anion. Noting this resemblance, Hawthorne suggestell lhat lhe
anion
could be considered isoelectronic with C,H; and should Ihere fore be capable of acling
as a w ligand in metallocene compounds. He and his coworkers then succeeded in
synlhesiUng rnetallacarbornnes. launching a new area of chemistry which is still being
actively invesligated: 1:16
+ FeCI:!_____.
[C!B,H11f-
+ 2CI-
+ [C.sHsl- + FeCI!---+ (ClByH 11 FeC5H_, r + 2CI+ BrMn(C0)5 ---+

+ Br- + 2CO
( 16.113)
( 16.114)
(16.115)
with the loss of one elecaron.

In cases for which strucaures have been determined. they have been found to correspond lo that
on the basis of metallocene chemistry (Fig. 16.5)).
Other heteroboranes such as
1ne ferrocene analogues. like ferrocene, are
may also be synthesized.l.l7 This compound may be regarded as one in which NH has
formally replaced a BHi- moiety of [B 13 H 11 )! - (also see Problem 16.41).
Structure Pre diction
for Heteroboranes
and Organometallic
C luste rs
In Chapter IS we observed that lhe

rule was adequate for prcdi<:ling
slubililies of small organomelullic duslers. In thl chapter we have seen thut Wade's
rulo:s allow us 10 make predictions abool borane slructures based on I he number of
framework electrons. n-.ese rules also are adequate for most carboranes, rnetallacarbor.mes, and other hcteroboranes.'"' Furthermore, organometallic cluslers thai are
not derived from boranes can be dealt with in a similar fashion. More sophisticated
extensions are required for complex larger clusters.IJ9
,,. Baker. R. T.; Delaney, M. S.: Ki. .. R. .. Ill ; Knolller. C. B.; Lana. J. A.: Marcltr. T . 8 .:
Paxson, T. E .; Tclta-. R. G .: Hnwlhome. M. F. J . A Chrm. Soc-. 1984. 106, 2965-2978. Long.
J. A.: Marcltr. T. B.; Bdonl<en. P. .: Hawthorne. M. F. tbHJ. 2979-2989. Knobler. C. 8 .: Marcltr.
T . B.: MizusaWR, . A .: Tdler. R. G .: Lore. J. A.: BcMkcn, P. .; Hawlhome. M. F. Ibid.
:!9'10-3004. Lana. J. A.; Marder, T. B.; Hawthorne. M. F. Ibid. 300ol-l010.
' " MijUa-. J.; Runsinlc.J.; Porosold, P. " "-"'"' Cf,m, IHt. EJ. Enl(l. 1991, JO, 17S.
u o O' Neob, M. E.; Wad<. K. ln M"ul /nu,rti<Nu...;th IJ<,nn
Gnmes, R.N .. Ed. : Plenum:
New York. 1982.
,,. Mirlaos. 0 .
a.,,,.;
M. P. 11<-r. Cttrm. R-.. 1984. 11. lll-lt9. Willes.

L. Ac-e. Cttmr. Rts. 1990, ZJ.
D. J.; Minaa.. 0 . M. P .. Slce. T.:
loron Cog Compounds
803
.J
."
tb)
h:l
101
""II
Fi g. 16.53 Sttuctun:s of <orne carboUyl mctullocenc o:ompoun<ls.

OiQrb<lllyl specie$:
M;
a 2. :snd M ; Co. II I are iNOCiectronic w ith
and cobaflocenium
ion: M Fe. " ; I ;,. iocltrunic with fen-occnitlm ion: lbl mm:d
a rbullyl-cyclvp:ntatlioon) l an:alocue
(crroo:ne. 11 I : tel mixc.J c:uboltyl-carbonyl
cumpoond. M Mn.
l!al and !b1 fmm Hawthorne. M. F.:
T. D. J. Am .
Cl,m.
t96S. IJ7.
from Adler. R. G.; Hawthorne. M. F. J .
S11<:.
1971l. 91. 1\174. Rcprocb:"d with permission.J
s.....
In the previous section we viewed the

anion ns a ligand analogous to
IC.tH., )-.
a more useful approach is to view [Fe(T)-C5 HsJI - as a replacement
for a BH frsmem. i.e. a species which. like BH . provides three o rbit:lls and two
ck-.:tmns. In other
we might prctlict that we can n:placc the BH unit with any
that is isuluhal with it ICh:tph:r lSI. Possibilities incluc.le lin addit ion to
FctCOI1
:-.lhCOI: . AIR. or Sn llhe tr.msition metal
.ore J.f.cft:cllon
four
hllr1 of II!. allll the nontransition
metal units arc four ck-.:trons sh.m of an o.>o:tt:tl. Similarly. une could imagine a CH
unil of a caroor..nc bciDG replaced by a species which can provitle three orbit:lls and
three eleclrons. Fitting this description are CO(COI,.
;md P. In Table
are listed
fragments and 1he number of electrons each can provide
suucture. You can construct your own table by remembering thai
to a
each trnnsition metal has twelve cleclrons associaled with it thai are reserved for
of twelve can be contributed lo the
nonframework bonding.o.oo Electrons in
fr:llllcwork llhus the
species above con lribute two elecll'Ons each, and the
IS-electron species contribute three: electrons. etc.). If there ure fewer th:ln twelve
electrons in lhe ff:l!!mc:nt , the ff:lmework musl make up Ihe difference [e.g .. Mn(C012
an
species. is nssigned a fr.omework contribu lion of- 11.
,.. Til< lr:>Mibon
nine o.tit:ols 10M' three p . :Kid five J )
ror honWng. ..... only
tine :on: a..ubk: ror ft:liTICWOflt bondq. The uoher sl . winch llousc: 1wctc ciJrons. arc used
ra bc>ntJit11t to cuo:malliptllls.
104
16 lnorgonic Chait>s, Rings, Cages, ond Cluslers
.. -
lpbl 16.2
Eletlrons ovoiloble for
ftom-otk bonding fo.
-ious orgOIIOO!Wtallic
ftogmenh
FJ'09fl*ll
Cr,Mo,W
Mn,Tc,Re
Fe,Ru,O.
Co,tth,lr
Ni,Pd,PI I
M( ,S-CsH5 )
- I
0 l
- 1
I
0 .. i
2
I
4
6
MtCOh
-2
0
M(C0)4
Frameworlt eleclrons (F) cquallhe number of metal valenCe elecii'Onl (MI plus lhc number of
c:leclrons donaled by lipnds (L) rr<ntos twelve (F M + L - 121.
One of our goals here is to be able to predict the structure of a cage or cluster from
its molecular formula. We do this by first finding the number of framework electrons.
'The structure will then be predicted to be closo. nido, or arachno if the number of
fr.tmework electrons is 2n + 2, 2n + 4, or 2n + 6, respectively. As an example let us
consider
for which n eqoo.ls Hve. The three BH units and the two
FetCO)) units contribute two elecuons each and the four extra hydrogen atoms
contribute one electron each to give a total of 14 framework electrons:
2 X 2 a 4e3BH: 3 X 2- 6e4H: 4 x I= 4eTotal
14e-
2Fe(C0h:
Fig. 16.54 Structure of

B,H,jFe(C0111,. !From
Grimes. R. N. In
Since n
S, we see thai there are 2n + 4 framework electrons and we predict a nido
strucwre which is found expe.r imentally. The square pyramidal s tructure (Fig. 16..54)
can be thought of as resulling from substitution of two BH units with two Fe( CO))
units in B5 H9 (Fig. 16.49a).
Let us apply these procedures to the nonborane molecule, Rh,(CO>u, for which
n equals six . Each of the six Rh(C0)2 units contribute one electron to the framework,
while the four exira CO molecules p rovide eiglll electrons:
Cilrmistry:
Wilkinson. 0 .. Slone.
F. C. A .. Abel , E. W .
&b.: Perpmon: Oxford.
4CO:
lli8Z: Vol. I. p HO.
wilh
permission.[
X
X
2=
Thus we have 14 framework electrons with the complex fitting the 2n + 2 categorY
and pcedicted to have a closo structure (Fig. IS. IO). There are two terminal CO groups
per rhodium and four bridging carbonyl groups which span alternate triangular faces.
Another method for obtaining the number of framework electrons starts by counting
the valence electrons of a.ll of the metal atoms and then adds all of the electrons
donated by the ligands:
6Rh:
16CO:
Q BH
I = 6eBeTotal = 14e-
6Rh!CO).: 6
9 .. S4e-
16 x 2
= 32e-
Total
- 86e-
Twelve of these electnons per rflodium (a total of n ) will be used for nonfroli11Cwork
bonding leaving 14 for framework bonding. Thus there are seven bonding pairs in the
loron Coge Compounds
805
framework corresponding to 211 + 2 electrons and , as above, a C'foso structure is

predicted. It is worth noting thut the IS-electron rule fails for Rll.,(C0) 1,, while Wude's
rules are entirely successful.
There are exceptions to Walle's rules. even among modest-sized clusters (see
Footnote 13S). In some cases large transition metals cause geometrical distortion. In
others. a kinetically favored structure may not be able to rearrange to a more
thermodynamically favored one . In still other instances the assumption that transition
metal atoms will use twelve electrons for external ligands is not valid. As with most
rules, one should not expect
to be fooiJl(oof.
The lx>ndlng capabilities of transition metal clusters (no nonmetals in the framework), based on molecular orbital calculations, hus been nicely summarized by
Lauher ffable 16.3), Within this table we see tbree struclures (tetrahedron, butterfly, and square plane) for telrnnuclear metal clusters. The tetrahedron is a 60electron cluster, while the butterfly and square plane clusters have 62 and 64 electrons. respectively. When we go from a tetrahedron ton butte rfly. one of the edges of
the tetrahedron is lengthened corresponding to bond breaking.
Tallie 16.3
Rolotion,ip betw....
9eometry, -1ecu1or
...t.i!al1, and duster
1 - -
No.
otams
18
34
48
Monomer
Dimer
lonclng mol.culor C"-ter

bilah
electrons
Trimer
3
Tetrahetlron
4
Butterfly
4
4
Square plane
Trigonal bipyrnmid
Square pyramid
Bicapped tetrahedron
6
Octahedron
6
Capped square 'pyramid 6
Trigonal prlam
6
7
s
s
c.a9Ped octahedron
17
2.4
30
3t
32
60
62
64
36
72
37
74
42
84
43
43
' 4S
49
-'
'
Exa...Pes
Ni(C0)4
Fe2 (CO)p
Os,(C0) 12
Rh4(C0) 12
Re4 (COii6
Pt4 (02CMcl1
Os,(C0) 16
Fe,(C0)15C
Os6(C0) 11
Ru6 (C0)1,.C
86
86
90
98
-r-
Lauher. J. W. J. Am. Chrm. Soc.

metals. !
tm, 100, 3)()5--.sJU. AU 1\"ameworit Moms re IJ'aMilton
,., Lluher. J. W. J. Am. Or.m. Soc.
tm. /00. ll03-Sll5.
;J! I.
w ;}.
-- ii ,;; ;1,
...
806
16 Inorganic Choins, Rings, Coges, ond Clusters
To .Jo this. two additional electrons must be added to the tetrahedron to keep aU
electrons paired. In fact this is a general principle: Addinc electrons to a closo
complex opens the Slructure, converting it to one o( lower symmetry. The bullerfty
s tructure results when an edge is removed from the tetrahedron.
If we add two electrons to the bullerfty structure. another edge is lengthened
(another bond broken) and we end up with a Square plane.
These principles apply equally well to heteronuclear clusters which can be illustrated with the trigonal bipyramidal cluster of ruthenium and sulfur, ((p-cymene))Ru)S2f
This 48-electron closo cation (24 electrons from three Ru atoms. 18
electrons from three p-cymene molecules. and eight electrons from twoS atoms) may
be reduced reversibly to the SO-electron square pyramidalnido c.l ustcr by adding two
electrons as shown in Fig. 16.55. Both the closo and nido clusters have been isolated
and characterized c.r ystallographically. The average Ru- Ru bond distance in the
c/o.ro structure is 2n.8 pm, corresponding to three Ru- Ru single bonds. The nido
structure has two Ru-Ru single bontls (m.3 pm) intact , and one bond severed as
shown by the long Ru-Ru diSlance (361.2 pm).
As you become more familiar with transition metal clusters (no nonmetal.s in the
framework) you will come to associate closo structures with numbers of electrons. A
trimer will have 48 electrons, a tetrahedron will have 60 electrons. a trigonal bipyrami.J
will have n electrons. and an octahedron will have 86. Some care is required.
however. as can be illus trated with Os3H 2(C0) 10 An electron count gives us 46 electrons rather than 48. If, however, we allow for one Os- Os double bond. the electron
count is as expected. In accord with this expectation. one osmium-osmium bond is
found to be shorter than the other two and the complex shows the reactivity expected
for nn unsaturated complex.
.2
s
Rg. 16.55 The Ru,S: core in (p-cymenehRu)S: (riaJ>tl ;,""' hs <lieu!ion [I p
cymene),Ru,s::f (len). The
annohed to
5ix-dectron ll:>nc>rs are not
pictured. Two-electron reducJion c:onvens lhe eornplex from dc>so 1u niclo geometry.
(From
J. R.: Rauchfuss. T. 8 .: Rheincolll. A. L. J. Am. Cllrm. S. 19119. Ill.
5733-57.)8. Rcp'Oduced ..nth
I
t42
Loc:lccmcy..-, J . R.; lt:tuc:hfuss, T. 8 .; Rltdrcold. A. L J . Am. Clwm. S. 1989, ///, S133-5738.
Metal Clusters
Cl.OSO
NJDO
..:.!?!..
ARACHNO.
807
Fig. 16.56 Structures nf

osmium cumplee wflkh
hnve seven pairs of skeletal
electrons. Each capped
triangular fncc adds twelve
electrons tu the tOiul
electron count. but the
number of skeletal p3irs
remains seven. Likewise

removing OstCO)) deletes
twelve electrons withcxlt
changirG the number of
skeletal p:>irs. The diagonal
lines show allcmute
geometries with 1hc same
total number of electrons.
!From McP:!nlin. M.
198-1. 1 .
Reproduced with
permission.)
(IUII:t
10.0tCOt, 1h1
1HO<cCOI 1!1-
Some of the beautiful relationships that c:ist!>.:twccn dt>.m .

an<! tll'lll'h""
osmium complexes are shown in Fig.
For lack of spa.:c we have not tou.:hc.J
on many subtleties associate<! with geomctryiborxling/electron counting pro.:wures
and the reader is encourage<! to consult more
sources.' ...
Metal Clusters1 4 S
Compounds containing mctal-mel<!l booos are as ol<l as chemistry itself (calomel was
known to the chemists of India as early as the twelfth century). The dimcric ruuure or
the mercurous ion was not conlirmc<l until the turn or this century ami in the next
oo
M. Pnlylwdrun t984, J, 12'/Y-121!1!.
,.. Minp. D. M. P.; Wnlcs. D. J . lntmdttC'Iitm It> Clu.<t<r Clrmri.TII')': Prentice Hull: E.rl(llcwuml
CliiTs, NJ. t'J90. Teo, B. K.; Zhang. H.: Shi, X. ltrtWJ:,
t\t911, 29.
Al>o <ce
Footnote 139.
'"" Cuuon. F. A. J.
Jut. 19113. 611. 7t3-T.!tl.
808
16 1norgonic: O.oins, Rings, Cages, and Clusters
hlllf-century discussions focused on lhe possibility that :zinc and cadmium might
pos...ess similar species. It WllS only some
years ago that the study of other
metal-metal bonds began in earnest; yetlhis
of inorganic chemistry has grown
at a phenomenal rate.
Metal cluster compounds can be convenientl y grouped into two classes: (I)
polynuclear carbonyls, nitrosyls, and related compounds; and (II) halide and oxide
complexes. The former group was included in Chapter IS. The second class will be
discussed in this section.''"'
Why do we separate clusters into two classes rather than deal with them as a
single croup of compounds? It is primarily becnuse they hnve unrl!lated chemistry.
Metal aroms in class I have low formal oxidation states, - Ito + I, while those in class
II are found in higher formal oxidation states, + 2 to + 3. The transition metals on the
right side of the periodic table (late transition metals) typically form class I clusters,
while those on the left-hand side (early second and third row transition metals) tend to
form class II clusters.
Ousters of metal atoms are more likely among metals that have large energies of
atomiulion (hence very high melting and boiling points). Thus the most refractory
melals IZr. Nb. Mo. Tc, Ru. Rh. Hf, Ta. W. Re. Os. Jr. and Pt) have the greatest
tendency to form metal clusters.
A second factor which must be considered is the nature of the d orbitals. The size
of the d orbitals is inversely related to the effective nuclear charge. Since effective
overlap of d orbitals appears necessary to stabilize metal clusters, excessive contraction of them will destabilize the cluster. Hence large charges resulting from very high
oxidation states arc unfavorable. For the first transition series, the d orbitals are
relatively small. and even in moderately low oxidation states ( + 2 ami + 3) they
apparently do not extend sufficiently for good overlap.
Dfnucleor
Compounds
The best-studied binuclear species are [Rc:,X8 )1 - ions. They may be prepared by reduct.i on (with H!.
or PIICOCI) of perrhenate in the presence of x-:
2ReO;
[Re1XsJ 1 -
X = Cl. Br, I. NCS
(16.1_16)
The most interesting aspect of these compounds is t heir structure (Fig. 16.57). which
possesses two unusual features. The first is the ext remely shon Re- Re distance of
224 pm compared with an average Re- Re distance o( 27S pm in rhenium metal and
248 pm in
The second unexpected feature is the eclipsed configuration of the
chlorine atoms. One might have supposed that since the short Re-Re bond requires
that the chlorine atoms lie at distances (-330 pm) which are less than the sum of their
van der Waals radii C-340-360 ppm). the st11ggered configuration would be preferred
than a cube). Collon
(the chlorine atoms would then form a square antiprism
explained both phenomena by invoking a quadruple bond. 101
Colton's rationale was as follows. The z axis of the ion is taken as t he line joining
the two rhenium atoms. Each rhenium atom is boodeclto four chlorine atoms that are
,., Conon. F. II. An.

1973. 1/, 22..S-23l. CotiOn. F. II.; Wahon. R. II. Mlllli/* lk>Js
Brt,._,n Mrllll
W'dey; New Yori<. 1982. Chi51dm. M. H.; Rolhwdl, I. P.
/mlfX.
Clltm. J!llll. 19, 1-72. Vorsns. M. D.: Nidlols. J . N. Ad.. lttnrx. Chrm. RaJIIIrm. t\186. JQ,
IU-222. Pol}"lwdron; t 9117, 6, 665-&0t
No.4.
In lhe Chemislryoi"Mdai-M<Ja!Mulliple Bonds,'' Chisholm. M. H .. Ed .). Fenske. D.:OIImcr. J.: Hac:hl;md.
J.: Mcnwcilc:r. K.
CJ.-m. lnl. EJ.
JJI88., 27, 12n-l2%.
on Concn. F. A. CMm. Soc-. Rrv. 1913. /2.
Metal Clusters
809
Fig. 16.57 The

or
tile
ion. Rc::Cii.- [From Collun.
F. A.: H11rris. C. 8. ltwrf:.
Chmt. 1965. 4 . )JO.
Reproduced with
permission.!
almost in a square planar array (theRe is SO pm out of the plane of the fourCJ atoms).
We may take the Re-CJ bonds to involve approximate
hybrids on each metal
utilizi'l: the dr'-.r orbit31. The metal d.,: and P: orbitals lie along the bond axis and
may be hybridized to form one orbital directed toward the other rhenium atom ano.l a
seccnd orbital directed in the opposite direction. The former can overlap with the
similar orbital on the second rtlenium atom to form a u bond (Fig. 16.S8al. while the
second hybrid orbital forms an approximately nonbonding orbital.
16.S8 Multiple
boodit11
woms: (a)
or a
" bon<! rrom overlap or

orl>it:al or each rhenium
atom. Cbl Form:uion or n tr
bond rrom overi:Jp or tile
d,. ortitnl ol euch rhenium
(It
Ulom. A second
1r
bond
forms in thc: r- plane. (cl

POliitivc uvcrlnp rrom d,.
orhituls 10 Conn a 6 bond in
tile cclips..'il cunfo>rmatiun.
C<h Zcru uverl:op uecurrintt
in the SJau:re.l cunro>r
mution. (In pan rrom
lbl
Cotlm. F. A. Ace. C/1mr.

Rrs. 1969. 1, !40.
Reproduced with
permission.)
I
Ct
I
I
I
I
0
(C)
(d)
810
161norga,.ic ChaiM, Rings, Cages, and Cluoten
The dr.: ami d orbitals of ench rhenium are directed obliquely towanl their
counterparts on the other rhenium and can overlap to form two 1r bonds (Fig. 16.S8b).
one in the xz plane and one in the yz plane. A fourth bond can now form by
"sideways" o verlap of the remaining two d orbitals. a dxv on each rhenium. the result
being a 5 bond . Overlap of the dxv orbitals .:an only occur if the chlorine atoms are
eclipsed (fig. t6.S8c). If the chlorine atoms are staaaered, the two d.,. orbitals will
likewise be staggered with resulting zero overlap (Fig. 16.S8d).
The Re-CI bonds in the complex may be regarded as dative bonds between the
Cl - ligands and Re' (d4) ions. The eight d dectrons from the two metals will occupy
the a bonding, two 1r bonding. and one & '>ending orbitals to form the quadruple bond :
hence the complex is diamagnetic. The model successfully accounts for the strength of
the bond . the short Re-Re distance. and the eclipsed conligurntion .
There have been many compounds discovered which resemble the
ions
in possessing extremely shon M- M distances. eclipsed conformations and, presumably. quadruple metal-metal bonds. The isoetectronic molytxlen um( lll species.
is known and both Re(ll () and Mo<IIJ form a large ser ies of carboxylate
complexes of formulas
Re: IRC0:14 X: . and
+ 2MeCOOH- Re..tCMeC01hCI4 + 4CI- + 2H*

Re 1 Ct: - + 4MeCOOH
Re..tCMeC0 1 )4 Cl1 + 60- + 4H +
Re..tCMeCOll4 Ciz + 4PhCOOH - - +
Re1 (PhC0 1 ).CI 2 + 4McCOOH
2Mo(C0)6 + 4MeCOOH - - + Mo 1 (MeCOJ4 + 12CO + 2H1
(16. 117}
(16.118)
(16. 119)
( t 6.120l
Structurally these ccmplexes (rig. 16.59) are clearly related to I

the only
.Silference being (for the rhenium complexes) the addition of ligands to overlap with
the met:ll dp hybrid orbitals which were nonbonding in [Re2C"'l! -.
Although Colton's molecular orbital scheme was largely qualitative . based on an
approa.:h involving a combination of atomic orbit als. a variety of theoretical
('
I
/c,
0 / '\.
o-o_c;/R
x-R<""
b
"--;;R.::_x
c-;-o
R_... 0
'\. /0
/0
c
I
........Mo-l-lo......
R_...
0 .,...,.1
O
'-,/
I
("
/'\,
l .,...,.o-jc.0
I ,x
, I X/1R-t
X
0
/c:,
R_.,
'/
c
M Cr. Cu
It
laJ
CI>J
tel
Jdl
Fig. 16.59 Molecular Slructurcs of some: cartuxyl:ue tomplc.us coni:\Jnina met41,-met:sl

bonding: Ia) Re- Re s :!:!0 pm. X Ct . Br. 1: tbl Rc-Re :!10 l'ftl, X s Ur. Ct. L:
H:O: (cl Mo- Mu
210 pm: !d) Cr-Cr 2lf> pm. Cu-Cu
pm. I. s H: O.
Rc-Rc bond lengths are
in<liidual
nn: known to arcuter ill:d.lr.IC)I.
t_,.......... o -j-c
.,...,.o
Metal Clunen
811
have confirmed the essent ial correctness of the az,...&z bonding model.'"' Experimentally determined electron densitiest49 are consistent with the quadruple bond picture.
PaulingUo has provided an alternative, valence bond treatment of the quadruple
bond involving spd hybrid orbitals and four equivalent bent bonds. His model also
explains the experimental facts described above and provides a good estimate d the
bond length.
The strength of the quadruple bond in dirhenium and dimolybdenum compounds
hilS been a matter of con'>iderable difference of opinion. Earty estimates of the bond
energy rnnged from as low liS 300 kJ mot- (weaker than a C-C single bond) to as
high as 1500 kJ mol- 1 (stronger than any o ther known bond). Recent studies indicate
that for 3d elements the bond energy lies in the 40-100 kJ mot- range. while for 4d
and 5d elemems values fall between 250and 450 kJ mol- 1,1SI The relative weakness of
these quadruple bonds may seem parudoxical, but we should recognize that comparing them with multiple bonds between small atoms which utilize p orbitals is not valid
because p orbitals provide superior overlllp and lead to inherently stronger bonds.
The [Re2Cl8f-, with its quadruple bond, is an example ofa complex with all of its
bonding molecul:lr orbitals tilled (Fig. 16,60c). Both & and & orbitals are near1y
nonbonding. however. and it would be expe.c ted thai electrons oould be added to the
!ilevel or removed from the &level without too much loss in smbility. l n keeping with
this expect:uion.
Fig. 16.60e) and
Fig. 16.60dl which have occupied antibonding orbitals have been synthesized. In addition. [MO:(SO>I)Fig. 16.60b) and
(oZ.,..,
_L
_j_
_L
_!_
_j_
_1._
,.JL1.
.l.Jl
..1...1.
..1._1_
_1_.1..
_j_
_1._
_1._
_1._
_1_
J .ll
JS
).1)
"
tR<:CI1 1:-
c\ un'flk J \J!ciii_,)J 11:.

fll)
tbl
tct
; l'ht,l-
k<:CI,t PM<!'>I,
t.Jt
I< I
Fig. 16.60 Qualic:uivc molccul:lr orbital diaarum for .tinuclear rhenium and molybder.Jm
complexes. All or chc bondina molecular orbitals are filled for [Re.Ct,.J'- (c) and a bond order
of -1 results from one a. awo " and one 6 bond. When dectrons are added 10 the 6 level,
the bond order is reduced as 'ihown for ldl and (e). Rcmovina eleclrons from the 6 bond aho
lellds to a low.:r bon.t order liS shown by (a) and (bl. (Tuken in
from Colton, F. A.
Chrm. Srx:.
1983. 12. )$ . Reproduced Wilh permission.(
'""'Hull. M. B. Paltht<kon, 1987. 6,

ZicaJeo-. T.; Tschinke, V.: BeeR. A. Ibid. 68>693.
B. E.; Clwl<. D. L. /hill. 69S-"104.
, .. Hino. K.: Suito. Y.; Bbard. M. Acto CryJttJ/fot:r S ct. D. l,.t. 17. 2164--2170.
ua Pauling. l- f',x:. Nttll. Ar..J. Sci. U.S.A . t97S, 72, 3799-JIIOI.
'" Ziqkr. T.; Tsdtinke- V.: Becke- A.
1917. 6. 6&S-693.
112
l6 lnarga11ie Chains, Rings, Cages, and Clusters
Fig. 16.60ul which huve less than full occupution of the 8 bonding orbitals huve been
prepared. The characteriUttion of W1CI.<ORI.<Rl1 (R Me.Et) with a W=W double
bond completed a series of ditungsten compounds with bond orders of 4. 3. 2. and
There are two metals, Cu(ll) and Cri ll), in the first tr.m'lition series which form
acetate complexes similar in structure to the rhenium and molybdenum cal'boxytate
complexes (Fig. 16.S8d). Like their Re and Mo analogues. the Cu and Cr complexes
are diamagnetic, indicating that spins are paired. They differ significantly from the
complexes of the heavier metals, however. The Cu-Cu distance in t he Cu(ll) (d9)
complex is 264 pm. which is act ually somewhat longer thon the Cu-Cu distance in
metallic copper (2S6 pm). It appears that the Cu- Cu bond in copper(ll ) acetate is
only a weak single bond resulting from pairing the odd electron on each copper atom.
The chromium(IJ) acetate molecule
long thought to have the same metalmetal bond length as the copper compound and thus have a similar weak bond.
However. its structure was redetermined and the Cr-Cr distance was found to be
236.2 pm. which is considerably shorter thun that found in metallic chromium
12.49.8 pm).U) In fact, the Cr-Cr bond has been estimated to be about 4S kJ mol-,
which makes it stronger than t.he Cu-cu bond.ll4 All of this evidence ond orbital
symmetry suitability might suggest that the Cr-Cr bond in chromium acetate is a
bond. Still, not eve.ryone is willing to go that far. The problem is that this
" quadruple" bond is estimated to be only about as strong as a typical Cr-cr single
bond.IH II appears that most participants in the debale have chosen to view the bond
as a very weak quadruple bond. Aside from this controversy. the chief interest in
dichromium compounds has been in the wide nlllge of bond lengths they display
( ISS-254 pm). Some of these are the shortest metal-metal bonds known and have been
dubbed "su per-shun bonds. The variation in bond length, which is dependent upon
the nature clthe substituent ligands. is in sharp contrast to the relative uniformity in
the length of quadruple bonds in the heavier congeners (Mo- Mo
204- 218 pm;
W-W"' 216-230 pm).
Among the more interesling metal-metal multiple bonded complexes are the
hexaalkoxo dinudear tungsten and molybdenum complexes, (M 1tORIJ (M
Mo. W):'"'
These complexes are

like polynuclear metal carbonyl complexes (class I)
btn are included here instead of in Chapter IS because they do not possess
metal-carbon bonds. A rich chemistry has been developed in which alkoxides rune-
tn 1\n\lcrsm, L. B.: CotiOn. F. A.;

0 .: Fana. A.: llslcy, W. H.; Kohh:lmmcr, B. W. S .;
WallCirl. R. A . J . Am. Cllrm. S. 191t, /OJ.
.,, Couoo. F. A.: O.:Boco-. B. Ci.; ul'r:ldc. M. 0 .: Pip>!. I . R. : Ucl<o. 0 . A. J. Am. Chrm. S'"' t970.
91. 29:!6-2927
.,. C:ll'uton. R. 0 . l fftWI(. Cllrm. t911. 20. 2J<It-ll42.

W Hull. M. D.
tm, 6, 679-634.
""Cbisholm. M. H.: a.t, 0 . L :
M. J. J . Am. O<m. StiC'. t989. Ill, S74-.586.
M.tol Clusters
813
lion as stabili:ting ligands for 12-electn>n clusters . .,, The alkoxide group. RO-. hus
two tiDed p orbitals capable of c.loooting 'It elec tron density to the mdal centers. Even
so. because these p orbitals are ligand centered . the complexes ure looked upon
coordinatively unsaturated and containing formal metal-met al triple bonds (a:..rl.
The
bonds are somewhat amllogous to carbon-carbon triple bonds. For
example. the metal-metal bond can undergo addition reactions:
+ 2X2
CJ, Br, ll
(X
(16. 1ZI )
(i-PrOlJMo=MO(O-i-Pr)J
i-PrOO-i-Pr
(16.121)
II is also possible to prepare (1-BuO)jWs CR (R Me, Et. Ph) compounds in which

the isolobality of CR and W(0R)3 is apparent:
+ RCI!!ICR
(t-BuOIJWaW(O-l-Bull
-+
21 1-BuO)lW=CR
(16.123)
dimerizes, existing in equilibrium

Recently, it has been shown that
with W,.(O-i-Prl12, a molecule which may be tho"'8h l of as an analogue of
butadiene: 1.59
\ ; ;0
w
_.wI!!
., \
0
0 b
0
+
\ / ;0
w
II
.w
o""/ \
0 0
o,.\ 1
w-o
o, \ 11\ ;.,.o
w---- w
o-'1 \ 11 \'0
o-w - o
(16.124)
1 \
0 0
The tel ramer has been shown to be flux ional such that the tungsten-tungsten double
and single bonds migrate about1he w. ring. At the same time, the two isopropoxide
groups at tached to each wingtip tungsten undergo proximal/distal exchange l Fig.
16.61 ). All of this motion taken together
come to be known
"The BloomiiJl!tOn
Shuffle" after the city in whil.:h it w.1s discovered. lllll
Trinuclear Clusters
The best-known
o l' noncarbunyl clusters conhtining three metal atoms are
the rtlenium trihalides [IReQ_,IJI and their derivatives. The
structural unit is
shown in Fig. 16.62a. Each rhenium atom is bonded to the other two rhenium atoms
directly by metal-metal bonds and indirectly by a bridging halogen llg;rnd. In addition,
m C1tisholm. M. H.
...... Cltrm. Int. Ed. Ens/1. t986. ZS. 2t- JO. Chisholm. M. H.: Clarlt, 0 . L:
Humpden-Smilh. M. J.: HoiTm:on, 0 . H. AnK<'"'. Clrm. lnl. Ed.
t989, 28.
C1tisholm. M. H.
Rt'. 1990. 1J. 4 t9-12S.
Me.
,,. McCullou$11. L G.: Sdwuck. R. R.: DeWan, J. C.: Murdzck, J. C. J. Am. Clwm. Soc. 1915. 107,
S91!7-S99ll.
t"' ChW>olm. M. H.: Cllll1c, 0 . L ; Humpden-smilh, M. J. J. Am. Clttm. S. 1989, Ill, S14-j86,
,.. Is it possible thlu tllis """"' ,..,.. p<.,.,_.s the: ume year lh:ll 1he Chiclau San d!omlsr.>pioe.l Jhc
"Supo:rbowf Shullle -?
814
16 Inorganic
Rings, Cages, and Clusters
"Tho Bloomington Shurfk
o...
o-w-o
w--w
o-w-a
/\
.Q..Q.
Fig. 16.61 Dynamic intrnmolecular rearrangement of w.(OiPrh: [From Olisholm.
M . H .; Clark, D. L . ; Hampden-Smith, M. J. J. Am. Cltem. Soc. 1989, Ill. S14-S86.
Reproduced with permission.(
tl
Cbl
Fig. 16.62 Rhcnium(lll) ctustcl'3: (a) The structural unit present in a Rclllll trinuclear
cluster. The positions marked 0 are empty in the triha!icles in the gus phase but have
coordin.11il1 groups in other silootions. (From Penfold. B. R. In Penpt'ctivu in Strll<'furaf
Chemistry; Dunit:z, J. D.; lbers. J. A.. E<h;.; Wiley: New York, 1968; Vd. 2, p 71.
Reproduced with penni$sion.l (b) The structure of solid (ReCI,l.r (From Colton. F. A. ;
Mague. J. T . ln11. Clrem. 1964. J. 1402. Reproduced with
tel The !Rc.,CI.,!'onion. (From Bertrand. J. A. ; Cotton. F . A. ; Oollasc. W. A. lntlfJI. Cllem. 1963.2. 1166.
'Metul Clusten
815
each rhenium atom in the triangular array is coordinated by two more halide lil)ands
above and below the plane defined by the three rhenium atoms. E:JCh Re(lll) has a J4
configuration which would lead to a par.unagnelic complex if only metal-metal single
bonds were present. The complexes are diamagnetic, however-, which implies that
each Re atom is doubly bonded to its rhenium neighbors.
In the solid state the halides retain this basic unit. but further bridging between
rhenium atoms by chloro ligands results in a polymeric structure (Fig. 16.62b).
Likewise.llissolving the halides in solutions of the hydrohalic acids leads to form:uion
of dodecahalotrirhenate(llll ions.
(Fig. 16.62c). in which additional halide
ligands have coordinated to the empty positions present in the Re,X., units. Other
lig:mlls (such as R3 P. Me:SO. or MeCN) can also coordinate to
positions. The
Re3 cluster is persistent in many chemical transformations. The bond length is
250 pm. which is indicative of strong bonding although weaker than in
Although common among carbonyl clusters, far fewer examples oftetmnuclear dusters are found among the halides and oxides. One example noted previously is
W410Rl 12 which forms by dirneri:z:uion
The tetrameric W4 (0Rl 1 has also
and
may be viewed as unsaturated .
been synthesized. Whereas
is saturatell. containing W-W single bonds !Fig. 16.63). tM
Quadruply bonded dinuclear compounds ulw can dimcrize to give tetramc:ric
molecules:
Tetranuclear
Ousters
116. 125)
+ KCl
Fig. 16.63
of
The
four-mcmn.:rc<l rinl! is nut
:101! it appear; from bonll length
<or.: alternating single and triple Mo-Mo bonds. t<>!
measurements that
Tetmnuclcar cluster units lrhoml>oillal Mo.). connected by OXYb'Cn atoms and forming
infinite
are fount! in
W.,(ORl,.
R
Ro...._IW .....
. . . I .....Cfl
- -W-OR
Ro. . .
....
,., Chisholm. M. H. : H10fTman. J . C.: Kirkpaarick. C. C .; L"Mclti. J .; Foiling. K. J . Am. Clorltl. s,.,.,
If\!
RO-W - - W
'*''
/IJJ, I>O'Jl-IJil')'),
M\.1...e:.t1cy. R.
T.
Tor.trtli . C. C. ln Rccntivit.\' uf
81Htd.r: Chisholm.
M. H .. E\1.: ACS Symposium Scric<
Antcric:on Chcmic:\1 Sucicty:
DC.
p 41.
McC:uicy. R. E. fn lllttr,:ani Cltrmi:rtry Ttmarfltlle* 21st c,,,/1/ry: Chisholm: M . H ..
ACS
Syntposium Series !II: :\"""'ican <.1>emical S<><:icty:
DC. 191!3: p :!73.
816
161no rgonic O.oi s, Rings, Coges, and Clusters
Ag. 16.64 The Slruclurc or

the
ion; e s Mo,
0 ,. Ct. (b) The slruclurc
or 1he
ions; e
Nb. Tu; 0 ,. Ct. Br. [From
Colton, P. A. Ace. Cltem.
Rts. 1969. 2, 240.
Reproduced wi1h
permission.)
(l)
Hexanuclear
Clusters
(b)
Clusters of six molybden um, niobium, or lanUIIum atoms have been known for many
years, predating the wori< with menium . There two types: In the first, an octahedron
of six metal atoms is coordinaled by eight chloride ligands, one on each face of the
octahedron (fig. 16.64a). This is found in "molybdenum dichloride," Mo6 CI 12 beller
formulated as [Mo6Cia)CI4 Each Mo(ll) atom can use its four electrons to form four
bonds with adjacent molybdenum atoms and can receive dative bonds from the four
chloride ligands.lM
Cotton has pointed out that a metal in a low oxidation state can adopt one of two
strategies in forming clusters. It can form multiple bonds to another metal , as in
!Re,x.J2 - . or il can fonn single boods to
other metal atoms. as in the
octahedrdl clusters. II is interesting that Mo(ll) adopts bolh methods (fig. 16.6S) and
that both structures have a cubic arrangement of chloride ions.
The second class of hexanuclear clusters also contains an octahed ron of metal
atoms, but they are coordinated by twelve halide ligands along the edges (Fig. 16.64b).
Niobium and tantalum form clusters of this type. Here the bonding situation is
somewhat more complicated: The metal atoms are surrounded by a very distorted
square prism of four metal and four halogen atoms. Furthermore, these compounds
are electron deficient in the same sense as the boranes-there are fewer pairs of
electrons than orbitals to receive them and so fractional bond orders of are obtained.
,.,
(b)
Fig. 16.65 A comp;uUon or !he lWO chtoro comptucs of MO(II ): (D) quadruply bonded
(Mo,Ct.J-: (b) singly bonded (Mo,cl,o/-. (From Cotlon. P. A. A. Cltcm. Ru. 1969.1.
240. Reproduced with pcnnission.J
,.,.
F.
Chrm. Rrs. 1,6f,l, 240. ,..-
Metal Clusters
Palyatomic Zintl
Anions and Cations
817
It has been known for nearly 100 years llwl

melals dissolve in liquid
ammonia in rhe presence of alkali merals 10 give highly colored anions.t6S In I he 1930s.
polyalomic anions (Fig. 16.66a.bl such :ts
and
were
idenlilied bul nol struclurally characlerized. Allempls al isolaring cryslals were unsuccessful because I hey
in solulion. This problem was overcome in 1975 by
slabilizing lhe calion of lhe sail as a cryplale (see Chapler 12), e .g. (Na(crypt)j,Pb,
and
which reduces !he tendency of lhe sal1 10 conver1 lo a
alloy.t66
Salls of polyaromic cations. such as
and TC:+. ure oblained from melts and
slabilized by large weukly busic anions such a.s AICt;:
Bi + BiCJ 3 + AJCI,(o:xcessl-+ Bi,(AICI4J,
(16. 126)
Since lhese homopolyalomic (Zim/) anions und cn1ions are devoid ofligands. !hey are
some1imes referred lo as "naked" cluster.;. In general !here is a good correlation
between eleclronic structure and seumclry as predicled by Wade's rules for lhese
cluslers. though some exceptions are known. Thus whereas
and
are
isoeleclronic. they have different slructures. I he lalter violaling the rules. Only a small
dislortion of lhe bismuth cation. however. would convert ilto the geometry observed
for lhe tin cluster
(b)
tel
Fig. 16.66 Some
(d)
Zintl ions: lnl
(bl
(d) TC:,'.
'"' Coobcu.l. 0 .: Crilchlow. S. C.: Durn<. R. C. In RU!Rs. cwm. tmJ

oft/w Moin GnMP
Cowley, A. H.. Ed.: ACS Sympo<ium Series 232: American Chcmial Sociely: Wa>hinaJon. DC. 1983: p 95.
,.. C<l<bell, J.D.
Rrv. ttas. &S. 38}-)97.
818
16 Inorganic Chains, Rings, CagH, and Clusters
Chevrel Phases
Ternary molybdenum chalcogenides,

are polynuclear clusters of special
interest. These compounds, oftetl called Chevrel phases, have both unusual structures
and interesting electrical and magnetic properties. An example is PbMo6 S8 , which is a
superconductor at temperatures below 13.3 K. The idealized structure may be thought
of as an octahedral cluster of molybdenum atoms (as in Fag. 16.65b) surrounded by a
cubic cluster o( sulfur atoms. which in tum is surrounded by a cubic lallice of lead
atoms. However. in the actual structure, the inner Mo6Sa cube is rotated with respect
to the Pb lallice (Fig. 16.67).16711 appears that this rotation is the result of very strong
repulsions between the negatively charged sulfur atoms (or sulfide ions) in one SH cube
with those in an adjacent cube. Thus. if lead is replaced by a more electropositive
metal (e.g. Etr), the calculated charges on sulfur increase and the tum angle
increases. Since the superconductivity is thought to be dependent upon the overlap of
the J orbitals on molybdenum. this prepeny may be "tunable" by appropriate choice
or metals.611
Infinite Metal Chains
Many highly reduced halides of scandium, yttrium, and zirconium have been found to
have infinite metal-metal bonded chains.l69 Zirconium chloride. for example, contains
double metal layers altematilll! with double chlorine layers (Fig. 16.68). It was dis
f"'9. 16.67 Structure of one of the Chcvrel compounds. PbMo,S.. (el Mo: (01 S; 101 Ph.
!From Collon. F. A. In
of
DonJs; Chisholm. M. H., Ed.: ACS
Sympo.ium Series ISS; Americlln Chemiclll Society: Washing10n. DC: 1981. Reproduced wilh
permission.I
101 Odlt, F. S.. ll; Sienko. M. J. """11 Cllm. 19110.19. I)S2-13S6. Po1cl. M. Chcvrcl. R.: ScrgtN. M.
Atta Cry:stullo/(r..
D t9110, J6. 1)19-1)22.
'"" Runlcu. J. K.; Lin, J. H.lnorg. Ch.m. t982.11. S-10. Co,.,.l. 1. D. J . Soml Sttt" Ch,.m. tlllll.
J9, 36-74. Saito. T. ; Yi11Tllm01o. N.: Nasnse. T .: Twbui. T.: Kobuyushi. K.:
T. :
lmolo. H.; Unoura. K. lnorg.
1990.19. 764-770.
""7jeb3fth. R. P. : Cornell. J . D. A. CJr,.,n. R ..s . 1989. 1!. :!56-:!6:!.
F. :
J .: l':lyr>e.
M. W. ; Cornell. J. D. In 1ctrnn Trtuuf<or in DH>I'JIY undt/o,. Solid Stut<':
C,mpmmJs
with Unusual ProJWrtit:s: Johnson, M . K.. Ed.; Advances in Chcmilry 226: Amc:rican Chemic;,!
Suciccy:
DC: 1990: pp 369-.389.
Condusion
819
Fig. 16.68 The structure o(

ZtCI. n reduced met.ll
halide system cont.linins

infinite metal-metal boncls
:showing double met.ll atom
layers nltemating with
double chlorine: atom
layers. (from CO<bell. J . D.
Rr:r. 19111 . 14.
Jl<c.
239. Reproduced
with
permissiOn. I
covered rather recently that many of the Groups JJI (3) and IV 14) hali.Jes. once
thought to be binary, are in fact stabilized by the presence of
atoms
(introduced unknowingly) such as h}drogen. carbon. or nitrogen. An example is
Sc.sa.N. once thought to be ScsCI,.. Its structure reveals an interstitial nitrogen atom
and consists of infinite pairs of chains in which
clusters are connected by
shared chlorine atoms (Fig. 16.69-dl and by shared metal edges !Fig. 16.69b).no By
exploiting the stabilizing role of inlerstitiul moms. systematic syntheses have been
developed for many new aoo interesting
including o ver 60 zirconium
chloride ph:lses.
Synthesis af
Metal Clusters
In the preceding <lescriprion of metal clusrcrs. synthetic reactions were given for
of reactions reflecrs in pan the facr that the
synthetic chemistry is not fully systematizeO-ofren an attempt to make a quudruply
bonded compound. for example. may lead to a doubly bonded one instead. Many
years ago Cotlon observed thai ... the srudent of cluster chemisrry is in somewhar
the position of the collector of lepidopter.1 or meteorites. s kipping observantly over
the countryside and exclaiming with delight when fortunate enough to encoumer a
new
m Aoo more recently . he has stated ... the most common method
of synthesis is some sort of thermally .!riven pm<:ess. quite often a
an.J thus
Jcsign an.J selectivity tend 10 be ahsent much of the lime. ""17: Even w . progress
lowurd rationul synthcs.:s cominues to be ma.Jc an.J. in punicular. applic:lli<m of the
principles of isolob:slity :m: proving 10 be:
uscfu(.m
Conclusion
An extremely wi.Je variety of compounds . r.1nging from metal-only to nonmetal-only

to those molecules that are mixed mo:tal/nonmetal. has been encountered in this
some. but not for others. The
,,.. Hwu. s .J.; Dudi. D. S. Cul'bcn . J. D.

171
Colwn. F. A. Q. Rra. Chtm.
t9M.
C/,.m. 19117 .?II. 41>9-473.

]!).
lY7.
m Colton. f . A.: WilkiMun. G. AJr11nr<tJ
Clrnni.m y. Slh ell.: Wiley: N<w Yurl<. 191111: p

ti!SS.
m Allams. R. D.; Babin.l. . /tH>rJI. Cll<m. 1!187 . 16.
(iCf)(Croy. G. L. In
Clruun in
Cmulysis: Galt'S. B. C. Ciucri. 1..
H . Ell>.: Et..:vicr: Atn:Uerdam t9111>; <.:haplcr I.
M. D.; Nicflods. H. N. Jim. lrwwx.
RtulitwMm t9116. Jll.
Snilo. T.:
Yoshiknwu. A.; Ya""'';lllll. T.: lmoto. H.: Unoor.a. K. ln"'ll CMm. t9!19. :x.
Cib<J.
re11cr. W. L. AJ Ors:ummtrt. Chtm. t9HS. 2-1.
Stone. F. G. A. In
Chrmistry:
TowurJ tire 21st Ctntury:
M. H. Ell.; ACS Symposium Series 21 1: American Cbcmical
Society: Washin&lon. DC. 19113: p 383.
cm.
820
16 Inorganic Chains, Rings, Cages, and Clusters
{b)
fig. 16.69 (nl The structure of "Sc,Cii' as it was first reported with stacked Sc6 octahedro
(black bonds) and bridging stacked SeC!, octahedro (black atoms and white bonds). The
poorly scattering nitrogen atoms are not located. (b) The correct structure of Scs(:I$N
>howing ScoCI,N units bridged by ScCI . The interstitial nitrogen atoms lie at the cemer of
the Sc. octahedra. Pan (a) shows several layers of a pair of these chains. If the nitrogen
we("C shown in (a) they would be stacked in the center of the two columns of stacked
black paroltelograms, o. [From Hwu, S-J.; Oudls. D. S.; Corbelt, 1. D. IMrg. Cl,tm. 1987.
16, 469-473. Reproduced with permission.J
chapter. All have had their descriptive chemistry systematized on the basis of structurnl principles. Pert.aps surpcisingly (and perhaps noll) metal clusters obey the same
rules as nonmetal borane clusters; metal-metal multiple bonds follow the same symmetry as those in organic chemistry, then go one beIter by allowing quadruple bond
formation: catenation, long thought to be an almost exclusive province of organic
chemistry has proved to be an extremely important aspect of inorganic chemistry. A
unified view of the chemistry of all of lhe elements is emerging as we approach lhe
21st century.
Problems
,J
16.1 Draw all of the structural isomers of

and draw all possible stereoisomers.
A.'ISUme that inversion at phosphorus is slow
16.1 Susgest a structure for P7 H, and its anion.
16.3 As indicated in the text. silanes are less stable than alkanes la11:ely because a facile
dccomposilion pathway is available: to I hem. Sugges1 a mechanism for the decomposition
of Si!H4
16.4 Compare the relative reactivity of silanes and alkanes toward nucleophilic attack. hydro_ _ _ lysis, Uf!d.halogenation
_ ._ __ - - .
Problems
821
16.5 Methods o( successfully synthdlizlna

orpnic polysilanes were dcveiC)flell
only in the last decade. Wilh 1he uill of refer ences given in 1his chaplcr. pr.'>Cnl u
synthesis for the homopolymer IMePIISi),. 11nd the Cop<)lymc.r tMcPIISi),(Me,Sil_.
[SiOi- J,,
... [Si.ol.lt.. and [SiO,J...
16.6 Draw struc:1urcs or [SIO.J- .
Enclose the r cpcalif!B units in brackels llnd tihoW lh<ll lhcsc empirical formulas arc correct. How do the ratios or oxygen to silicon correlate wilh 1he degnre or pQ(ymtrization in
silicwes (i.e. discrete ions compared to chains Compllrcd to double chains compared to
infinite sheets compured 10 thrccd imensionnl frJmeworksl?
16.7 Both nosclite and ultrumurine conlllin AI,Si,.O,. fo rmula units. WhUI is 1hc charge on this
unit'? In nddition, nosclite conulins u sulfate ion un<l ullrJm:lrinc has 11 pcr.wllidc ion. How
many sodium ions arc present in uch overall empirical formula'!
16.8 a. Why ore such
useful us lubricants?
disparate sub"'unces us tole. dny, unci llf"Jphitc slippery and
b.. Althouah 1he structures o( tulc :1nd muscovite :arc r:11her similar. l hc latter is much
harder and unsui1ablc liS a lubric;mt. W hy? Should these minerals h:lve uny propcnies
in common?
16.9 Gem quality beryls ate aquamarine !blue).
lgrccnl. and f!Oidcn beryl Likewise.
amethyst is a violct-<Cllored silica, and $:1pphirc lblucl lind ruby (rch ..-c nlumin:a. YeJ
pure beryl t8c,Al,Si.0 101. silica (SiO:). and aklmina IAI 10 ,) are
Explain.
16.10 Althoush olivine is a common rocl:-formina mincr.JI ond quanz is the commonest o(
they are never found tooethcr. Explain.
16. 11 Muscovite and biotile h:lve very simil:ll' comp<)siwns. Why is one " while mica"
the
other "bluck mica"? In 1he some vein, Ullc i5 while. chrySolite is white ubcstos.
crocidolite is blue usbestos u.nd amosile is a groybrown asbe>IOS.
16. 12
to molybdenum( VII and turocslenCV II. chromium!VIl docs not h:le

sive polyanion chemistry. Sugest an
extro-
16.1J In llddition to chromate and dichromate, trichromalc, 1Cr,0 111 t'-. exists. Poslubte a
structure for the trichromute ion. Compare Its 5lructurc to Ihat of tP,O,.,J' -. Trichrom:lle
hydrolyzes in wUier. Predict the hydrolysis prolluc1s.
16.14 From an inspection or the li111Jrcs, or even better. from molecular models. dc1ermine the
geometry or Ihe coordin:Jtlon sphere (c:uvity) In cuch ur 1he hercropuly
in
the ch::oplcr.
16..15 Wrile babncetl cquotions sllowina 1he folluwina conversions:
u. IVO.J'- to [V,Ool' -
b. [H: V 100,..) 4 - h> [VO:I"
16..16 Cons ider the slruc:ture of the union, [CcMo 120.d-. This saructure muy be thought of as
consisting of twelve MoO. octohcdra or six Mo,O. aroups. The former
7:! oxygen
atoms and the Iauer S4. yet there are only 42 OKygen atoms in the slruc:ture. Explain. How
m11ny terminal oxyJ;"n u1oms per molybdenum nrc present? How muny bri.Jging
atoms are p4'CSCnt? Whutls the coordlnution number ofCe<IV) nnd or C'...:h kind or oxygen
atom? What is the point JVOUp o r the cn1irc union?
16. 17 Determine the point aroups o( the cyclic phosphincs in F"111. 16.34 und 1he phosphorus
oxides or Fig. 16.36.
16..18 The iminob<>roliiC. i-PrB=N-t-Bu, trimcrizes to (i-PrBN-t-Bu)) which has a Oewarboruine type struc:turc. 114 C0f1'41al'e this
to Ihal of bo<uine.
The cyclic trimeric
16. 19 Boroxincs result from the condensation of boronic ucids,
anhydride ofmcthylboronic acid is (MeBO)). Give a balonced equation for the reaction o(
(MeBOI, with w-.ucr. (See Brown. H. C.; COle. T . E. OrxuHJmrlallic$ 191.5. 4.
ll<
Paclzokl, P.; von Plolho. C.; Schmid, G.; lloe$e, R. Z . Nutld[urS<:h. D: AnvrR.
1984. J9, t069.
CJrs:. Clotm.
822
16 Inorganic Chains, Rings, Cages, ancl Clusten
16.:!0 Phospham.
CDn be ob1uined by lhc reac1ion o( red phosphorus wilh ammonia.
Write a balanced equation for its produclion from JheSe two reogenrs nnd druw a possible
srrucrure for lhis cross-linked polymer.
be prepared from the reacrion of
16.21 Monophosphazenes, RJP-NR'. are well known :md
and R'NH,. Write a balanced equarion for lhis reaction.
16.22 As discussed in the chopler. trimeric phosphazenes are usually planar bur can be forced
out of rhis geometry. In contrast. benzene derivatives arc striclly planar. Discuss Jhe
reasons for lhe greater flcxibiliry of lhe phosphazenes.
16.23 Draw all of the possible isomers. excludinglhose 1ha1 are N-N bonded, of S ,(NH),_,,
16.24 The classlcru argument concerning the equivalence oflhe posi1ions on rhc benzene ring is
based on lhe existence oflhrec (ortho. meta. paral isomers ofxylcne ldimclhylbenzene).
How many isomers are there of dimethylborazinc?
16.25 Complexes (0C)4 fe(P4 0.) and (0C))Fe(P40,J, form from lhe reaction o( Fe(C011 and
P40 .. Suggesl struclures for rhese complexes. Would you expecl similnr reactions wiJh'
P4 0 10? (See Walker, M : L .; Mills. J. L. lnorg.
1917. 16, 3033.)
16.26 Phosphorus pentoxide is an excellent dchydraring agent. For ex:unplc. il atn be used to
remove water from nilric acid. Write a chemical equarion for this reaclion .
16.27 Suuest a structure for P40.S synthesized from P40
10 and
P. S ,u-
16.28 Elhane reacts wilh oxygen 10 give carbon dioxide and warer. Diborane reaciS wi1h oxygen
10 give boron(lll) oxide and warer. Write balanced equations for these two reactions.
Look up heats of formation for the reoctnnts ond products o( these reactions and calculate
lhc heats of reactions. Considcruble work was expended in evalua1ing borunes us highenergy fuels in rhe 1950s. Compare elhune and diborane as fuels.
lli.29 II has been StJGilCSied"' that sci

in the endo form nther lhan an exo "crown"
form whh Se(t) flipped down bcause of reduced lone-pair repulsions bc1ween Sc<2).
Se(J). Sc(6) and Se(7). Sketch !IIese rwo forms of Sei Add lone pairs to your drawing and
indicate how stabilization occurs in the endo form.
16.30 What structur es do you predict for 1he anions. B:!H1 and B1 H;?
16.31 Diborane is widely used in organic ch'fllistry (hydroboralionl 10 convert
imo
alcohols. Consult un organic book and show reactions for this convc,.,ion. Whl is lhe
advantage of this method'/
_..16.32 Complete the following equaJions:
a. [PNCJ,h
h.
e.
d.
. .--/
Me,NH-
+ 2R1P ----+
+ 2NH1 .. + excess Cl 2 -
16.33 Assuming that the exlemal H-8-H angle in B! H

angle:
u. Calculate the
renecrs 1he interorhiral
s and p characler in 1hesc
b. Calcula1e the sand p characler remaining for !he bridging orhiral> .

c. Compare the value from (bl wilh 1he experimcnlnt intcmol :1nglcs.
16.34 Use Wade's rules to predict Jhc SltueJUres of lhe following:
a. B,H,(CO):Fc(CQ))
b. C,B. H.Pt(PE,h
Problems
16.35
1h:
elcctron-counlinll rules und show 1hut1hcy nre
the nit.lu llvenex structure shown below. '"'
823
wilh
II
QBH
e c-Et
16.36 Wbal is lhe maximum bond onlc:r you would predicl for neutral W, Cno ligands)?
16.J7 Wbal bond angle would you expect fOf" M -O- R in "" alkoxidc compkx? How mi&hl
1his bond """lt change 3>.,. llonalion rrom the p ortH!als o r oxygen incn:ases?
in !Os:Cixl:- are
1See A&asbr. P. A.: Cotton. F. A.: Dunbar. K. R. :
Falvello. L . R.; Tetrick. S. M.: Walton, R. A . J . Am.
Sue:. 1986. 108 .J&.'O.I
16.38 The cbloro groups in (Re:CI.I: - are eclipsed. b111 1he dlloro
Off..- an
16..J9
lbotlhe procluc:l of Eq, 16.12S COnl3illS Mo-Mo p;Urs lh:tl ;are .Joubly bridged by
chlorine and Mo-Mu p:>irs tluu are not. If this molecule conlains
sinaJe :tnd
lriple bund.'l, which bunds are which?
16.-IG The struc:hwe of Ni,O,S:cPPh,t. i unulocous 10
16.S.S). 171 De1crminc if
rules un:
of
for this mole.:ule.
cFig.
I6.U Which of the following.Jo you lhink would be mus1 likely In vicw or isolobal consi<lera-
lions and W:tde' s rules'/ !See Linle. J. L.: Whi1cscll. M. A.; Kesttf', J. G.; Foiling. K.;
Todd. L. J . lnu'1/. Cl,m. 1990. !II, 811-1-l!OII.)
3
X
a. Bi
b.
(, p
01
d. P
Bi
QBH
J6..U In addition to the phospha:o:.enes <lil<CUSSC:d in Ibis chapter, u l;orge croup of hdero<)'dic
compound. known as
hlL been chai'3Ctcrize.J. These contain P- N single
bonds :and muy cont:lin plloopboru< either in the +) or + S oxidulion slates . Draw
structures of (C1,PNMel: und (CIIOIPNMc(,. PhusphOt"USII III tri und telr:tphosphazanes
have bec:n slllbilized by plncins ...phenylene
between ud,l:lccnt nilrogcn :tiOfllS.
Give one e.'ulml'feof roeh and dr:tw i1s
(Sec Baren.ll, J. M.: Haltiwanger. R. C .;
S<!uicr. C. A.; Norman . A. 0 . ltmrt. Clttnt. 1991, Jf), 2342-2J49.r
J6.4J Dnlw structures rl>l' t.hc four possible l'IOIT\ers of

Snro.Jon. L. G. l nurfl. Clwm. 1990, 29, 295-302).
. (Sec Beck. J. S.;
o> Swr>her. R.
t911S. 4 , IIK!-li\JO.
,,.,
G.: Sinn. E.;
D.: Olmcr. J.:

1::!77-t:!%.
lt.:J.; Grirno:A. K. N.
H. : Menweikr, K. Anll""' Clwn. lttJ. EJ. Enfll. 1988. Zl.
Chapter
17
The Chemistry of the Halogens
and the Noble Gases
At
first thought it
appear incongruous to discuss lhc chemisuy of the halllf:ens
and the noble gase.s together. The former includes the violently reactive fluorine which
will oxidize il1l save a half dozen elements. even reacting explosively wilh a compound
as stable as water. while the latter family contains the inert gases' neon (differing from
fluorine by one proton and one electron per a tom) and argon (<K. argos. lazy. uscJessJ.
In one important aspect. however, they are very slmilar. namely their ionization
energies: F 1681 kJ moJ- 1 (17.42 eV). Ne = 20111 kJ mol- 1 (21.S6eV). Ar = IS20 kJ
mol- 1 (IS .7S eV).2 The difference between these two families lies in the inordinate
.Jisparity in electron affinities. The common tendency to emphasize the differences
between the ramilies and dismiss the similarities results from a lack of recognition of
the two types of behavior (gain vs. loss of electrons) and the fact that the noble gases
are unique only in the discontinuity of their ionization energy-electron affinity (or
el.:cuonegativily) function . Thus it is oflen said or implied that the electronega tivities
of the noble gases are low or nonexistent . equating electronegativity with electron
affinity. II is true that the noble gases have no negative oxidation states . But. on the
other hand. electronegativity also means a reluctance to release electrons
in this
regard the noble gases. as a group. are unsurpas!led. In fact. the limiting factor wilh
resard to which noble cas compounds form. or do not form . seems to be the extent to
which a given noble gas atom is willing to share e lectrons with an ;nom o f another.
more electronegative element .
The halogens (except fluorine) exhibit both electron-accepting anc.l electron-releasing behaviors. Since they resemble the noble gas elements only in resard to
electro n-releasing. this aspect of the c hemistry of the two families will be d iscussed
first. The more familiar acceptance of electrons by halogens is discussed later in the
chapter.
:oo
' Sc:venl names have: been applied 10 the Group VIllA (IH) clcmcncs. The tcnn ..inc:n" is illllpt)lic:llblc
to the JfOUP liS a whole til is used above as a $pific adjcclivc: of neon 3nd arson. not "" a aroup
eppdhuion)
a1 leasl lhtc:c members of !he famiy 1ft ""' inert The name ''noble ps
a
10 react ralher than COflllkt obtlcnlion. lhos pan)ldi..: the use of this term in
dacribing lhe chemisuy of cenajn m$ls sudl .. aold _, ptuinum.
>One could abo drllw a comparison bctWn the noble IMU :ond the albli mel:lls basal on lh<ir tow
dcaron allinilia. HoweY<r, lhe elr:dron ui!Wiics
psa appear :alwp 10
whereu the alkali mccals have smal bOI liclite rxothnmic electron nllinitics k:xlirw 10 some
chemislty basal on acaplanc:e of electrons (O>Iplcr 12).
Noble Gas Chemistry
Noble Gas
Chemistry
The Discovery of the
Noble Gases
The Early Chemistry

of the Noble Gases
825
Although the observation of a line in the sun's spectrum as early as 1868led worker-s
to posiUiate the existence of an unknown element in the sun's atmosphere. the
isolation in 1889 of helium from the mineral cleveite by heating was not recognized as
a related phenomenon. The first definitive work was by Lord Rayleigh. who noticed a
discrepancy between the density of "chemical nitrogen" and that of atmospheric
nitrogen." The former was obtained by chemically removing nitrogen from various
nitrogen oxides, ammonia, or other compOunds. The Iauer was obtained by removal
of oxygen. carbon dioxide. and water vapor from air. The difference in
was not
great: 1.2572 X 10- l g cm-l for "atmospheric nitrogen" compared with1.:!506 X
w-l g cm - l for chemical nitrogen" under the same conditions. The careful work
necessary to establish this diffuence has often been pointed to. quite rightly. as an
example of the importance of precise measurements. Unfonunately. too often the
emphasis has been upon the number of signific:sntligures rather than the realization by
Rayleigh and Ramsay that the difference was chemically significant. Their arguments
concerning the significance of the ratio of specific heats of the noble gases <C,.fCr =
1.66P and their rebullal of various arguments advanced by their critics show as much
chemical insight as the gas-density argument. if not more .
Ramsny and Rayleigh socce..."tted in isolating all of the noble gases except rndon
and in showing that they were inert to all common reagents. They also discovered the
identity of alpha particles and ionized helium.
It is often assumed that the noble gases had no chemistry prior to 1962. This is true
only if one restricts the definition of a chemical compound to (I) something containing
"ordinary" covalent or ionic bonds und (21 something which may be isolated and
shdf. If either of these criteria is dismissed. much
placed in a boUle on the
important chemistry of the noble gases can be recognized prior to the 1960s.
If an aqueous solution of hydroquinone is cooled while under a pressure of several
hundred kilopascals (equals several atmospheres) of a noble gas [X = Ar. Kr. XeJ. a
is obtained. These solids
crystalline solid of approximate composition
are p..hydroquinone clathrates with noble
atoms filling most of the cavities.s
Similar noble gas hydrates are known <Fis. 17. 1). These clathratcs are of some
import:mce
they provide a st:lble. solid source ofthe noble gases. They h11ve also
been used to effect SCIXr-Jtions of the nohl.: gases since thcr.: is a certain sele.:tivity
exhibited by th.: duthr:ues.
Of p:u1icular interest is the ell'ect of noble gases in biological sysu:ms. For
example. xenon has an anesthetic effect. This is somewhat surprising in that the
conditions present in biological systems are obviously not sufficiently severe to effect
chemical combination oft he noble gas (in the ordim1ry sense of thai word). It has been
proposed that the structure 'Of water might be altered via a clathrate-type interaction.
Although clathrate formation and dipole interactions are perfectly acceptable
subjects for chemical discussions, chemists feel more at ease when they can lind stable
compounds formed from the species being studied. A logical approach would be the
linclatingthw the 8"-' IOOS! be mon:uomic since energy is nbsorbc.J only by translalklnal modes. not
by vibrtion or
(cf. C,JC.
1.40. 1.36. and t.J2 for N:. 0:. and Br:.ll.
For n discuuion of the earliest wor1t on the noble
see Wolfendcn. J . H. J.
EJuc. t969.
46, $69; Hiebert, E. N . In
C<Jfnpnnmls: Hym=. H . H . Ed. ; University of Oliaao:
Olicaao. t963: p J.
'The pcrccnt..,es o( available cavities thw are lilted by noble ps aiOms 111e 6rl. (Ar), 67-74% tKrl.
3
and !WI. !Xc).
826
17 The Chemistry al lhe Halogens and the Noble Gases
FOg. 17.1 The struclure of

lhc: xenon hydrare clathrnte.
The xenon nloms occupy
lhe c:enlcrs of regular
pcnraaonnl dodecahedra of
wnler molecules
(cf. Fi&. 8.8).
inveslig:uion of I he noble gases for possible Lewis basicity. Since 1he noble gases are
with halide ioos which can be strong Lewis bases, it seemed reasonable
that noble gas adducls of strong Lewis acids might likewise exist:
F-
+ BF3
BFi
(17.1)
Ne+ BF3
NeBF3
(17.2)
+ BF3
XeBF 3
(17 .J)
Xe
Thorough studies of solutions of xenon in boron trichloride and boron tribromide were
undertaken. A phase study of the melting point of these systems as u funclion of
showed no evidence of compound formation. The Raman
of these
mixlures are identical to I hose of pure BX, indicating no noble gas-boron trihalide
intcrnctions.
An alternative approach 10 the formntion of true chemical compouno.ls of the nob!.:
g"dses is sugges1ed by two lines of I hough!. (II From an
point of view. 1hc
is capable of
s1rong.:s1 Lewis acid is the bare pm1on. H . so if uny or the noble
exhibiting basic behavior il mighl be eX(l'!Cted 10 lin so with H l tWI HlO. ):
He+H+- HeH
(17.-1)
Ar + H + - ArH+
( 17.5)
(2) From a simple molecular orbital diagram

as given in Fig. S.1. it might be
supposed lhat four electrons would result in a nonbonding condition but lhat any
number of electrons less than four would resull in some bondins though not necessarily in an integral bond order. Spectroe;copic: evidence for species such us HeH ami
ArH has been obtained from a mixture of hydrogen und noble gases
through
gas discharge lubes. Similar
can take place between two noble gas utoms if
energy is supplied to remove the necessary electron:
He+ He....:.!.:.. He;
(17.6)
Na ble Gas Chemistry
827
Kr
+ Kr
Kr;
(17.7)
Ne
+ Xe
NeXe
(17.8)
The noble sas hydride ions should have a bond order of one and the diatomic noble gas
ions should have a bond order of one-half. Neither type can be isolated in the form of
salts of the type He H x - or HeiX- since the electron affinity of positive helium. etc.
is greater than that of any appropriate species X. und so such snits wo uld spOntaneously decompose:
+ F1
(17.9)
+ HCI
(J7.10)
2Hej F - ----+ 4He

ArH CJ - ----+ Ar
Although the above reactions may seem to be of lillie interest to the chemist. it has
been found that in similar ps-phase reactions. xenon behaves as a nucleophile.
forming the methytxenonium ion. CHJXe. The C-Xe bond in this ion has a strength
of 180 !: 30 kJ mor 1
The Oi.scovery af
Sta ble, lsola ble
Noble Gos
Compounds
Although there had been

that some of the noble sases might form compounds. unsuccessful auernpts to oxidize krypton und xenon with fluorine in the 1930s
essentiaUy put 3 hnlt to such specul3tion. cspeci.11ly in view of the success of valency
theory in relating stability to Riled octets. This worship o( the octet is all the more
surprising in view of the fact that compounds whh expanded vnlence shells were
already known ror over two-thirds o( the remaining nonmetnls!'>
In the ear1y 196<k Neil Banleu was studying the properties of platinum hex
alluori.Je. 3n extremely powerful
agent. In fact, by merely mixing dioxygen
with platinum hexafluoride. it is JlQS<iible to remove one electron from the oxygen
molecule ano.J isolate the product:
(17. 11)
ionization energy o( dioxygcn. lll!O kJ mol- 1 ( 12.:! eV),
BartleII rc:llize.J that the

is almost io.Jentical to that o(
l liO kJ mol- 1 t12. 1 eVJ. Furthermore. the
.Jioxy!!en
shoukl be ruuyhly the same
as X.: ion. and hence the lallice
energies of th.:
compoun.Js shoukl he simil.ar. He mixed xenon an.J
pluinum hcxulluvriilt: with the rc\ull that an imm.:.Jiatc reaction took pluce with
fuomativn of a yellow solitl. l!:tS.:il on the
vf &ases thai reacted. Bartlett
the reaction is not so simple as was
suggested the formulutivn xe(PtF,,r , 7
once thuught. and the product has been formulate\) variously as Xe[ PtF,J +
Xe( PtF, b . Xe(PtF.J, (I < x <:!).or FXe JPtF,J - + FXetPt! F 11 J-.
t he
experimental .Jifliculties in chaructcrizing the products of the reaction there was no
.Joubt whatever that a reaction had taken place and the myth of inertness was
shallcre.J forever.
w;n he discussed rurthot Iuter on thil chupcr anoJ in Ch:opccr t8. hul ror now it may be
bc>ul a dozen noM>Coals :ore known wilh v.llcncc llhdlstby convenlion:ll clcctrcn-puiri,.;
ron!Uism.t conomna rrom tO to t4 ck:ctrons. B. C. N. 0 . unoJ F 11\UfC 5lrictty <lbcy the OCicl ruk.
7 &rtlcu. N. Prnc. Clk'm. S. 1961, 11/l. For" review d the orty chemistry d
""' Uarttcu. N. n.Jc.,,..,..,
/J/1. l . Nule th:u pure Xc JI'IF.C rorms only if 1 bi'JC c..::css d
inen SF. is ildtlcd u a .Jiluo:nltGr:lhoJm. L. Ph. D. TheJis. Univcr'<!y or Caliromiaac Bcrttcky. t,711.
o. cite..! in the rd'lnJ1tt in fwlnolc 8).
Thr. (lllin1
"'J.
828
17 The Chemistry of the Halogens and the Noble Gases
The fluorides of the
Mixing xenon and fluorine and activating the mixture by thermal. photochemical. or
similar means result in the producticn of fluorides:
Noble Goses8
Xe+F1 --+ XeF2
(17.11)
Xe + 2F1 --+ XeF4
(17. 13)
Xe + JF1--+ XeF6
(17.14)
The chief difficulties in these reactions (once the proper equipment for handling
elemental fluorine at high pressure has been assembled) are not the syntheses but the
separations. All three products tend to form (Fig. 17.2). Xenon difluoride can be
obtained either by separating it rapidly before it has a chance to react further (by
freezing it out on a cold-linger. for example) or by keeping a high Xe-to-F, ratio. The
heXllfluoride is favored by large excesses of fluorine and low temperatures, but some
XeF4 is present which must be separated. The best production of XeF6 is obtained
The
using gases at low pressure and a "hot wire," a nickel filament at 700-800
reactOf" is cooled in liquid nitrogen. The most difficull compound to prepare pure
is xenon tetrafluoride since even optimum conditions for its fOt"mation thermally
(Fig. 17.2) will result in concomitant formation ofXeF2 and XeF6 The use of dioxygen
difluoride at low temperatures and pressures provide XeF4 in high yield and purity:9
c.
(17.15)
The chemistry of krypton is much more limited than that of xenon. Apparently
only the difluoride forms directly from the dements. Attempts to make helium. neon.
and argon fluorides have been unsuccessful. Radon should react even more readily
than xenon. but its chemistry is complicated by the difficulty of working with a
ng. 17.2 Equilibrium
800
pressures of xenon Huorides

as a runction or temperuture. Initial conditions:
t25 mmol Xc. 122S mmol F1
per liter. AI higiM:r Xe to F,
ratios tiM: Xc:F,. tliminisiM:s
considcrJhly and
the rem:ining lw<> curves
shirt to the lc:ll. lfrum
Selig, H .
Chem.
1967. /. 403. Rc:protluccd
with permission.)
Sqlpcb. K.; Lentz, D. Prog. lnofB.

9
Nielsen. J. B.: Kinkead. S. A.; Punon. J .
191%, 29. t67-202.
Eller. P. G. lnurx. Clr.!m. 1m. 29. 1779-t780.
Noble Goa Chemistry
829.
compound of such exceedingly high radioactivity. Nevertheless, the formation of

compounds with fluorine was shown conclusively shortly after the discovery of xenon
compounds. but their exact natures were not elucidated. More recently radon chemistry in solution has been studied (see below).
Banding in Nable
Gas Auorides
There are currently two approaches to the problem of bonding in noble gas compounds. Neither is completely satisfactory, but between the two they account
adequately for the properties of these compounds. The first might be termed a valence
bond approach. It would treat the xenon fluorides by means of expanded valence
shells through promotion of electrons to the Sd orbitals:
Ground state: Xe = [ Kr) Sr4d 10 Sp6
Valence state: Xe = [ Kr) Ss24d' 0 5p6 - "Sd"
For XeF1 n = I and two bonds form; for XeF4 n = 2 and four bonds form: and for
n = 3 and six bonds form. Using the arguments of VSEPR theory (see Chapter
6 and further discussion below) the resulling electronic arrangements and structures
are as follows:
Preclicled
Electron
&peri-l
Compound
pain
liybridization
sJrvclure10
sl1vc:ture
XeF2
XcF4
5
6
7
spJd
splJl
Linear (TB P)
Square (octahedral)
Nonoclahcdral
(capped octahedron?)
Lineur
Square pl:ular
Unknown exactly,
but not octahedral
splJ)
The use of Gillespie-s VSEPR theory has allowed the rationalization of these as
well as several other structures of noble gas compounds tFig. 17.3). One of the signal
successes of this approach was the early prediction that Xef6 was nonoclahedral (see
Chapter 6). The most serious objection to it is the required promotion of electrons.
This has been estirooted to be about 1000 kJ mol- 1 (10 eV) or more for xenon. a large
amount of energy. Furthermore. J orhitals tend to he diffuse and their importan.:e in
nonmetal chemistry is a mutter of some controversy (sec Chapter II!).
An alternative approach to bonding in noble gas compounds is the molecular
orbital approach involving three-<:enter_ four-electron bonds. Consider the linear
F-Xe-F molecule. ASp orbital on the xenon can overlap with fluorine bonding
orbitals (either pure p orbitals or hybrids) to form the usual trio of three-<:entered
orbitals: bonding. nonbonding, and antibonding <Fig. 17.4). Filling in the four valence
electrons
+ F:!J>, + f 29,) resulls in a filled bonding orbital and a filled nonbonding (lo a first approximation) orbital. A single bond (or bonding MOl is thus spread
over the F- Xe- F system. A second p orbital at right angles to the first can form a
second three<enter F- Xe- F bond (XeF4 ), and the third orthogonal p orbital can
form a third three-center bond (XefJ. The nature of the p orbitals involved in the
bonding allows one to predict thai XeF1 will be linear, XeF4 square planar, and XeF6
Ul The
is !hat of the atoms: the geom<'tiY in parenlhcSCS refcn to the lljli:COimatc

oC KIJ oC I he valence shell elcc1rons.
830
17 The Chemistry of the Halogens and the Noble Gcses
Lin<ar molcadc
tlrcc I'IO<lbondil>&
clo:cllcol pairs at !he points dan oquilolcnll
trionsk
5quan. p!On3r - l e willl <wo nonbondins

elo:cllcol pairs. one above oncl one below tbe
plonedthemole<iUie
(bl
F
(<)
or
F"rt.r
Xc
Oillon<d oaallednln wllh a nonbonding

ekCUOn pajr either a11he cenu:r of foc:c or tbe
rnidpcMnl ofllD odie
., t
F
F
py,.,;,w mok<ulc wilh.

nonbo!OO& dcruo<l polr prolt\ldina from the
!d)
- a!he pynmid
Trigonol pyr.unidol molc<ule with a

nombooding ctuon pair pro<rudlng from the
ope of the pyramid
I two """bolldq

clccuon pairs above an4 below the piDnc of!he
pcrllson.
Fig. 17.3 Molecular shapes predicted by simple VSEPR lheory. Bond aneJe vulucs reprcscru
experimental results where known.
Nable Gas Cl>emistry
Xc
CGLX]X)
831
00'00
00
00 .... -+I00 00 00 -tt-
-foo
...&
Xc
Fig. 17.4 Moleculur orbital diugrum (or F- Xe- F
mer bonds.
octahedral. The first two predictions are correct, but the last is not. On the other hand,
difficulties with promotion ene rgies are avoided. However , in a pure 3-c-4-e model.
the entire molecule is held together by only three bonds.
Structura l Data fo r
14-Eiectron Species
The number of species isoeleclronic with XeF6 is quite limited. The anions
and TeBri- are octahedral. Both IF6 and
are nonoctahedraJ.II JO<Iine
heptaHuoride and rhenium heptaftuoride may be considered isoelectronic with these
species if they are all considered to have 14 valence shell electrons or awoximately equal steric requirements. Both have a pentagonal bipyrnmidaJ structure (see
Fig. 6. 12). Most interestingly. the XeF; union, formed by the Lewis acid XeF.:
(17.16)
is the first example of a

ion (Fig.
It can be
rationalized in terms of five bonding pairs to fluorine atoms in a plane with :1 lone pair
above and below the plane. The lone p;airs :1ppc:ar to be "locked in" to the axial
positions as the molecule is not fluxional .
is the i.s oelectronic XeF6
The molecular saructure of
hus been u vexing problem. In the solid, XeF;
and F" ions
The former
live bonding nnd one nonbonding pair and is
therefore expected to
a square
with the lone pair occupying the sixth
position of the id ealized ocaahednan. Experimentally. this is found h> be the case. In
the gas phase. however. the structure is much more perplexing. from bo ah an experimcmal and a ah.:uretic:ol view. Elcctr.>n dill'r:lctiun
inJic:ue that the molecule is
a sli&hlly tliswrted
t hat is protmbly "soO" with
to defonnation.
There are no m.:asurnblo: dipole moments, ruling out (urge . .
J istonions. The
model that is currently acceptet.l is that of a stcreochemically
molecule that
rnpiJiy passed from o ne nonoctahetlral conlit:uration to :mother.
Th.: perfectly octahedral spedcs conform to th" expect ations based on the simple
MO derivation given above. The
tluoride species do not, but this
difficu lty is a result of the oversimplitlcul!ons in the method. There is no inherent
necessity for delocalizcd MOs to be restricted to oclahedral symmetry. Furthermore,
it is possible to transform delocnlized molecular orbitals into localized molecular
o rbitals. Although the VSEPR theory is oOen couc hed in valence bond terms. it
depends b-olSically on the repulsion of
of like spins. anc.l i( these are in
localized orbitals the resulls should be comparable.
II 8cxh lbe Of.;' ond BrF; ions ate OCIDhalnll. Qww<:, K. 0 .: Wiloon. W. W,; Chirobl. R. V. :
San.lcn. J . C. P.: S<brobilccn. C. J.

Cllr,. t!I9G. 29. l50f>-lStl.
Ovislc. K. 0 .: Cl.w1is. E. C.: Oixoro. D. A.: Mercier. H . P.; S:Jn.kn. J. C. P.: SchruWccn. C . J. J.
Am. Clwm. Soc. 199t, 1/J. llSt-3:!61.
832
17 T11e Chemistry at the Halogens and the Nollie Gases
As wilh many inorganic systems. the differences belween alterruuive interprelalions is more apparent than real. Favoring lhe purely octahedroil molecule will be
reduced promo1ion energies) and reduced sleric requirements. If lhese two constraints are relaxed. a slereochemical ly aclive ("hybridized") lone pair is favored.
probably as a result of beller overlap and stronger bonds.
Gillespie14 first discussed lhe problem presented to the VSEPR 1heory by the
perfec1ly octahedral species such as SbBJ{- ,
and
He pointed ou11hn1
steric interac1ions between the large halide ligands will be of considerable impor1ance.
(The Br- Br distance is approximately equal to the sum of the van der Waals radii and
a seven-coordinate" struclure with a large lone pair occupying one position would be
unfavorable .) He lherefore suggesled that as a result, the seventh pair of electrons
resides in an unhybridized s orbilal Inside lhe valency shell. As such it would be
s1erically inactive except for shielding the valence eleclrons and loosening them from
27S pm , compared with that
the nucleus. The somewhat leoglhened bond in
expected from addition of covalent rndii, 2SO pm, is consonanl wilh !his interpretation
(as it also is with a bond order of Jess than one from a three-center bond). In most
fluorides the reduction of steric factors allows the lone pair to emerge to the surface of
the molecule, al1hough perflaps Jess than it would in a four- or five-coordinate
molecule; hence these molecules appear less distorted than might have been expected
(see also Chapter 6).
There are two essentially isostruct.u ral cation/anion pairs that are not
electronic: They differ by a pair of electrons that could potentially be slereochcmically
active lone pairs.IS These are BrFt/BrF;; and l f'i 111=; . Simple VSEPR theory would
predict an octahedron and a square antiprism (or closely rclaled eight-coordinate
structure) for 1he cations. The anions might be expected to be a distorted octahedron
(:BrF6: cr. 1he isoelectronic :XeFJ and a dis1or1ed square antiprism (: If;). However . bromine is smaller than xenon, and even !he larger iodine atom apparently
reaches (as does xenon in :XeF;I its coordination limit with eighl fluorine atoms.
Thus lhe anions are also a perfecl octahedron and a perfect square anti prism: They
differ from 1he corresponding c:nions only in having longer X-F bonds. as might be
expected if steric crowding of t he fluorine atoms forces the nonbonding pair of
electrons into a shielding, centrosymmetric s orbital.
O ther Compounds
of Xenon
Allempls to isolate a stable xenon chloride have no1 been very successful. T wo
chlorides have been identified, and both are apparen1fy unstable species observable as
a result of trapping in a mu1rix. The radiooclive decay of
in KICI4 :
1291CI;
- - + 129XeCI4
+ p-
(17.171
has been used to produce xenon tetrachloride, characterized by means of the

Mossbauer effect (see Chapter 18) of the gamma emission from 1he resulting excited
Use or !be s orbilal in slercochemically ec:tivc rhybi'Uhcd.') cr1>il:lis requires r.W.inlllhe CIIC'll)' of
lhese eltrons 10 Ihal cllhc bondinll oct>i&als. 'The use d cfr4)1y. hiJtl..,eray d oct>itls :alsa requires
... ineralsc in
dtctron """'lll' f'lowelina or holcs'1.
14 Gillc:sp, R. J. J. Chrm. E4ur:. tm. -fl, 18. More recent 1rea1mcnu can be found in
R. J .
Soc. Rn. 1992.1/,59-69 and GlllesJX. R. J.; Haraill.i,l. Tlrr VS/'R MDikl o/Malfi:U/or
Grcmrtrr. Allyn and Becon: BoSI041. 1991.
IJ
" For !he dcl<rmnation
or the sll\ldln of IF0.
prolllem. and appropria1e

4. Ellgl. 199t , J(), 816-318.
a discussion oflhe BrF; /BrF0 and tfi:/tF,;

rda-ences. S Ma!Uaub. A. R.; Scppell. K.
Chrm. llt1.
Noble Gos Chemistry
833
stale. Mixtures of xenon and chlorine that were puul through a microwave discharge and immediately frozen on a Csl window ut 20 K gave infrared evidence for the
existence or
Careful hydrolysis of xenon hexafluoride produces Kenon letralluoride oxide:
(17.18)
Complete hydrolysis of xenon hexaftuo ride or hydrolysis or disproponionation of

xenon lelr.llluoride produces the trioKide:
XeF6
+ J H 10 - Xe0 3 + 6HF
+ 12H1 0 - - + 2Xe0 3 + 4Xe + 301 + 24HF
(17.19)
6XeF4
(17.20)
Xenon trioxide is highly explosive and thus renders any intentional Cor unintentional)
hydrolysis of these xenon lluorides potentially hazardous. Alternative sour<'eS of
oxygen to form the oxyftuorides have therefore been proposed:
+ NaN03
XeF6 + OPF3 -
XeF 6
XeOF4
XeOF4
+ NaF + FN01
(17.21)
+ PF 3
(17.2.2)
Xenon diftuoride dioxide cannot be isolated as an intermediate betwcrn the partial

hydrolysis to form
and complete hydrolysis to Xe03 but may be prepared by
combining these two species:
(17.23)
II may also be preparl by treatment of an excess of Xe0F4 with cesium nitrate: 17

XeOF4
+ CsN0 3
Xe0 1 F 1
+ CsF + FN0 2
By comparison. hydrolysis of xenon difluoride
(17.24)
only in decomposition:
(17.25)
Huston has systematized much of this type of chemistry in terms of the

L.ux-Fiood definition of acids a nd
Isee Chapter 9). The biller is one of
highly specialized definit ions that may be very U!oeful in a restricted area but not in the
the xenon lluorides are the
ucceptors.
more generul case. In the present
while they in turn lluoridut c the oxide donors. II iK possible lo construct a scale of
relative acidity: XeF6 > Xe0 2F4 > Xe03 F 2 > Xe04 > XeOF4 > Xef 4 > Xe02F 2 >
Xe0 3 > Xef:. wherein any acid can react with any base below il to produce an
intermediate acid. Thus. in general. XeF6 is the most useful and XeF2 the least useful
fluoridator. When XeF4 is used in place or XeF6 , the reactions are slower. II!
Xenon lluorides are also excellent fluorinators, though not so reactive as KrF 2
(see below). They are orten "clean," the o nly by-product being xenon gas:
2(S0 3h
+ 3XeF 1
----.
3S 20 6 F 1 + 3Xe
(C6 Hs)z5 + XeF1 - - + (C6 H 3),SF2
+ Xe
(17.26)
(17.27)
"'Cl-risle. K. 0 . : Wihcn. W. W.
Clu-m. t981. 17. ll'X>-1297. Nkben, J. B.; Kinkcal. S. A.;
Eller. P. G.
CM 19M,19. 362t- l622.
"Clvisle. K. 0 .: Wilson. W. W. buNt. Chmr. 1981.21, 3763-3768.
HU5l0n.. J. L /n<>f6. Owm. 1m.11. 68$.
834
17 The Chemis!Ty of the Halogens ond the Noble Gases
Sometimes the fluorination occurs with displacement of a by-product:
2R 3 SiCI + XeF2
__.
2RJSiF + 0
+ Xe
(17.28)
Even more interesting is the production of the xe; cation in antimony pentaftuoride as
solvenl. It was first prepared by reduction of Xe(ll). Many reducing agents are
including metals such as lead and mercury. or phosphorus trifluoride, lead
monoxide. arsenic trioxide, sulfur dioxide, carbon monoxide, silicon dioxide. and
water. Surprisingly. even gasemt& xenon may be used as the reducing agent: 19
Xe + XeF+
Xe;
(17.29)
Alternatively. one can view this as an acid-base iinstead of a redox) reaction of u basic
xenon atom undergoing a nucleophilic auack on an acidic xenon cation to form the
diutomic cation (cf. the reaction of Xe + CH). page 827).
As mentioned above. xenon trioxide is an endothermic compound which explodes
violently at the slightest provocation. Aqueous solulions are stable but powerfully
oxidizing. These solutions are weakly acidic ("xenic acid") and conwin molecular
Xe03 . When these solutions are made basic. HXeO; ions are formed and alkllli
hydrogen xenates. MHXe04 , may be isolated from them. Hydrogen xenate ions
disproponionate in alkaline solution to yield perxenates:
2HXe04
+ 20H - -
+ Xe + 0 2 + 2H 20
(17.30)
Xenate solutions may also be oxidized directly to perxenate with ozone. Solid pcrxenates are rather insoluble and are unusually stable for xenon-oxygen compounds:
Most do not decompose until heated above 200 c. X-ray
structures
h:IVe been determined for several perxenates. and they have been found to contain the
ion. which persists in aqueous solution (possibly with protooation
octahedral
to
Treatment of a perxenate sail with concentmted sulfuric acid resulls in the must
unusual xenon tetroxide:
(17.311
The tetroxide is the most volatile xenon compound known with a vapor pressure of
33011 Pa 125 mm Hg) at 0 c. The structure of the molecul.: is tetmhcdral as is the
isod.:.:tronic 104 ion.

The xenon-oxygen compounds an:: extremely puwcrful
solution as shown by the following 0 values:
H,Xc06
XeOJ
in add
Xe
The nature of the species and the values of the potentials arc not as well characterized
in basic solution, bul the oxidizing power seems to be somewhat less:
1.17
HXeO:-
---...1
XeOOW
)
"'S1c1n. L.; Henderson. W. W. J. Am. Clttm.
x-::1980. /02,
Noble Gas Chemistry
835
Like the fluorides. they :u-e relatively "clean" reagents. Unfortunately, the explosive
propenies of Xe03 have resulted in less work being done with them.
Xenon forms stable compounds only with the most electronegative elements:
fluorine (X = 4.0) and oxygen (X - 3.S), Of with groups such as OSeF_, and OTeF5 that
contain these elements. Reasonably stable, though uncommon , bonds are known
between xenon and both chlorine (X
3.0) and nitrogen (X 3.0). Bis(triftuoromethyl)xenon.
(XcF, 3.3), is known but decomposes in a matter of
minutes.
Xenon hexafluoride can act as a Lewis a cid. It reacts with the heavier alkali
fluorides to form seven-coordinate unions, which in tum can rearrange to form eightcoordinate species:
MF + XeF6
__.
M+[XeF7
(M Na, K, Rb. Cs)
(17.32)
2M+[XeF7)-
M2[XeFJ + XeF6 (M Rb, Cs)
( 17.33)
The octalluoroxenates are the most stllble xenon compounds known; they can be
heated to 400 c without decomposition. The unions have square antiprismatic geometry . They. too. present a problem to VSEPR cheery analogous to thal of XeF6 since
they should also have a stereochemically active lone pair of electrons that should
lower the symmetry orthe anion. If the steric crowding theory is correct, however . the
alums coulll fon:e the lone pair into a stereochemically inen s
presence or
Ofbital.
Xenon fb>rides can also act ns fluorille ion donon.
Lewis acills react with
xenon lluorilles to yielll the expected compounds. but since hOih the cal ionic and
anionic species can form ftuorill.: brillges. the stoichiometries may appear strange at
times:
XeF6 + Ptfs--+ XeF;PtF6
(17.34)
2XeF 2 +AsF 5
Xe2 F;AsF6
117.35)
XeF. + 2SbF,
----+
XeF;Sb 1 Fj'1
(17.36)
F.vcn compounds with

'imrlc Shlichiumcrrics may be more complex. as in
the .:ase ,>f
"hid1 has hullt
cutiun\ and uni<>ns:
[ ][
F
1 \
I
F
Xc
X.:
'\
F
F F
I' F
I:
F - A; -F-..U:-F
;'J
;'J
F I'
I' F
]'
Bar!len's comrouoo li'IJge 1127). thuua;h still in,ompletely understood, is lhought to be

or this type. Krypton difluoride funns unaloguus compouoos such as KrF AsF;,
KrFAS:Fj'1 KrFsbF;. KrF'.Sb:F11 anll Kr:F)SbF;. and these tocether with
the parent Krf: were the only known compounds 0( krypton kno"'n until
: AJ.M.atuu. M.: Hotluvo.,y. J. H.: Hope. F.. G.: Schrubilccn. G. J. J. CMnr. Sue.. Vul/tHt TruN.
t991. :!1131-211.14. Sdwo!Jilgcn. (). J. J. Cll<'tn. SH'.. Chrm. Ct>mmult. 19118. 86l-US. 1501>-1508.
836
17 The Chemi.stry of the Halogens and the Noble Gases
Reaction of HOzNH+ salts of [AsFJ- or R,<J=N adducts of AsFs with KrF2 in

nonaqueous solvents lead to salts characterized as [HCsoN - Kr - F]+(AsF;J and
[R,<J=N- Kr- F]+[Asf";l (Rp- CF3 , <;F,, n-C3 F7 ). Krypton fluoride has proven
extremely useful as a fluorinating agent: It is SO kJ mot- more exothermic than
fluorine. F2 1 It may be used to raise metals to unusual oxidation states;21
8KrF2 + 2Au 2KrF+ AuF6 + 6Kr
KrF+ AuF; 06-&S 'C AuF, + Kr + F2
Bond Strengths in
Noble Gas
Colnpounds
The Chemistry
of Radon
Table 17.1
Bootd llrenglhs in noble gas

conopouncls (kJ mol- l)
(17.37)
F2
(17.38)
As might be expected, xenon does not form any strong bonds. but it does form
exOihermic compounds with fluorine. Some typical bond strengths arc listed in Table
17. 1. Banlctt22 has shown that such values might have been expected by extrapolation
of known bond energy in related nonmetal compounds.
Since radon is the heaviest member of the noble gas family it has the lowest ionization
energy, 1037 kJ mo!- 1 (10.7 eV), and might be expected to be the most reactive. The
radioactivily of this element presents problems not only with respect to the chemist
(who can be shielded) but also with respect to the possible compounds (which cannot
be shielded). On the Olher hand, this radioactivity provides a built-in tracer since the
position of the radon in a vacuum line can be ascertained by they radiation o( 214Bi.
one of the decay products.n It was found that when a mixture of radon and fluorine
was heated. a nonvolatile product was formed, possibly an ionic radon fluoride.
Similar experiments with chlorine mixtures ten the radon in volatile form, presumably
unreacted. More recently it has been found that radon reacts with various halosen
fluoride solvents (BrF3 , BrF,, and CIF,) to form a species in solution which remains
behind when the solvent is volatilized. It is quite possible that a Rnl+ species is
present. Although the charge is not known with certainty, the radon may be present as
a cation in soiUiion since it migrates to the negative electrode under certain circumstances. but also towards the positive anode under Olhers. indicating the possible
formation of Rn2 , RnF. and RnF).
c"""""""' _
land . - Bond -BY

1
XeF1 XeF4 , XeF6 I'
Xe03
84 : ,. ':! J
:
:
KrF2
-} ., f'.Kr:..F :e;.:
} . .
.., 1
t,->ee-;o\
...___ , ... - - ....
J . H.: Scflrobitgcn, G. J. J .
22
Srx:.
--:.I
Comm. 1975. 623.
Banlcll. N. EnJnwour 1963,88. J . II is ink:nstingto nolc that Bar11eu did nm usc: isoetccaronic
series in his exlrapolalion. Furthermore. aiJhoush his exlrapolaaioos prOYide quiae
vab:s for XeF6 and XeO,. they lc:d 10 muclltoo hiah a value for KrF1 .
U The a and /J r.>diation of;mRn and the finland second daulhiers will 1101 pcnc:lr:l!e the V"dCUUIII line.
Halageno ;,
Halogens in Positive
Oxidation States
lnte rhalogen
Compounds
Oxiclotion States
837
In addition to the dihalogen

X:, known for all or the halogens in the elementul
state, all poss ible combinations XY are also known conlllining two different halogen
atoms.z In addition there are many compounds in which a less electronegative
halogen atom is bound to three. live, or seven more electronesutive halogen atoms to
form stable molecules. The known interhalogen s are listed in Table 17.2.
Several trends are noticeable from the data in the table. The bond strengths of the
interhalogens are clearly related to the difference in electronegativity between the
component halogen atoms. as expected on the basis of Pauling's ideas on ionic
character (Chapter S). Furthermore, the tendency to form t he higher fluorides and
chlorides depends upon the initial clectronegativity or the central atom.u Only iodine
forms a heptalluoride or a trichloride. Not shown in Table 17.2 (except indirectly by
computation from the values) is the instability of certain lower oxidation states to
disproportionation :
SJF Bond energies: 1390
21: + IF,
298
Gain in bond energy - 250 kJ
(17.39)
+ 1340
mor I
This tendency towards disproportionalion is common among the lowe,. fluorides of

iodine and bromine. The behavior or the four iodine: fluorides presents a good picture
or the factors imponant in the relative stabilities. Both IF and IF, tend to disproportionate (the former to the extent that it cannot be isolated), not bec::tuse ofweakllC$Sin
Table 17.2
Increasing axidation .,....
..
<
0
0
0
0
XY
IF (2n.8,.
XY,
IF, (-271)
BrF (249.4)
CIF (248.9)
10 (207.9)
BrF, (20 1.2)

CIF, (172.4)
XY,
IF7 (231.01
IF, (207.8)
BrF, (t87.0)
OF, ( - 142)
(10,1:
BtCI (215.9)
IBr ( 175.3)
F1 ( 154.8)
a. <239.71
sr; (190.2)
t,
(148.9)
p ortital electroncpivitics, Table S.6.
Vallld in parentheses are bond eneraies from ,\ppc:ndix E (kJ
mor
1
).
34 Since the most >bible isolq>c or ...wine hu o

or only 8.3 hours. the eherislry or 11Us
IWogcn 11M 1101 been sfudkd exlcnsivdy. In lhe folowi,. discussion ccnc:rolilics rn:>dc obou1 the
hBiotlcns may or ""'Y nol lndlldc: :uraUnc. In lhe prexnl inslancc AIBr and AICl have bc:en
prepared. Sec the discuuOt of aolalinc: cllcmislry b.llc:r In INs chaptu
.. Slcric racoon may lllso be impor1MI since
10 rhal of lhe
arorns.
stability alao patallds Jhe
sac: o( lhc cc:nlr.IIIIIOm
838
17 The Chemistry of the Halagens and the Noble Gases
bonding ( IF has the strongest bond of any of the interhalogens!), but because of the
greaJer number of bonds in the pentalluoride to which they disproportionate. AI lhe
other extreme, the heptafluoride, while stable, is a reactive species (it is a stronger
fluorinating agent than IF,) because of the weaker bond energy (resulting from both
steric factors and resistance to the exuemely high oxidation state on the part of the
iodine). Bromine fluoride likewise disprOpOrtionates, but BrFl and BrF, are stable.
Chlorine forms a monofluoride, trifluoride, and pentafluoride.
The cornpelitive forc.es lending to stabilize high or low oxitlation states can be
readily rationalized. The simpliSiic stacement: "The tendency to stabilize high oxidation stales in compounds XY., is favored by high eleclronegativities of Y (usually
fluorine) and low electronegativities of X (I he heavier halogens)," is d(/initely not
wrong; but does it explain for you the relative instability of IF (with lhe s trongest
interhalogen bond, see above)?26 Consider the following reaction to o xidize a halogen
monohalide to a trihalide:
X-Y + Y - Y - Y-X-Y
- , _,
(17.40)
2 >< 13< - 4-<booi!Jie<

) Vli'T-ml-
It is obvious that no great change in bond order occurs in this process and so any
cnthalpic tlriving force must result from I he quality of the bonds. A simple analysis of
ionic resonance energy (11u;). in terms of partial charges, ral ionalizes !he relative
stability of the monohalide and the trihalitle. Assume that the ionic resonance energy
that increases the quality of the bonds may be equated to simple M:ldeluns or
coulombic energy:
.ftu.yy ..
E..E.xv,
(17.41)
Case I. Sv is approximately the same in XY and XYland Sx = 38y. This is a good

approximation for Y = F, an element with high values of both n and h. i.e .. 3 hi!!h
inherent electronegativity but low churge capacity; it becomes saturatctl wirh negative
char(:!<: easily. It is also a good approximmitrn forn large. soft iotlinc. X '" I. whkh.:un
irs posicive charge to
three fluorin.: atoms. In
ck::orly.
31ix.SV >>lix8v, and the t rihulidc is f:worctl.
Case II. Sx is similar in XY and XY l and since Sx lily,........,.. 8v.....,.....,.. "'
38y,........,.. This becomes an increasingly good approximation as Y becomes larger wiah
lower values of both a and b. und the large, sort, central atom
anti
harder. In this case the monohalide is favored .
Exactly the same result is obtained if the initial electronegativity or the centrdl
hulogen is assumed to be higher in a higher oxidation st ate. and 6x and ionic
resonance energy are lower. The same arguments apply equally well to all of the
oxitlalion states:
:!0 Stt
the discussion or u,., insbbility of CaX in O>aprer 4.
Hologeftl in Positive Oidotion Stoles
839
Note that the more ionic the bood, the le$S important the apparent distinction
between 3-c-4-e bonding and VBT becomes. because the weaknesses of' both methods
of modeling the bonding decrease when one goes towards the Umit o( a .. purely ionic
bond."
The intertlalogen compounds obey the expectations based on the VSEPR theory,
and typical structures are given in Chapter 6. One compound not included there is the
dim eric iodine trichloride, in which the iodine atom of the monomeric species appears
to act as a Lewis acid and accept an addit ional pair of electrons from a chlorine atom
(Fig. 17.5).
The molecules Br2 , 12 , and ICI s how an interesting effect in the solid. Although
discre te diatomic molecules are still distinguishable, there appears to be some intermolecular bonding. For example, the molecules pack in layers wilh the intermolecular
distance witlrin a layer 20-80 pm smaller than the distance between layers. Within
layers "molecules" approach each o ther much more closely than would be indicated
by addition of van der Waals radii but less than that of norm31 covalent radii (Fig.
17.6). At the same time there is a slight lengthening of the bond between the two atoms
forming the nominally diatomic molecule . It would appear that in the solid some
delocali;zation of electrons takes place. making a simple. single-bonded molecular
structure no longer completely appropriate .
Polyhalide Ions
II has long been known thai 31though iodine hols a rather low solubility in water (0.3 g
kg- 1 at 20 "C), it is readily soluble in aqueous solutions of potassium iodide. The
Fig. 17.5 Molceubr

structure of 1!0..
in
JFrum Boswijk,
K. H.: Wicb<nsn. E. H.
A cw Crystnlln11r. t9S4. 7.
4t7.
with
rtermissiun.l
F'.g. 17.6
structure
o( iodine. The molecules lie
\
... \
in parlllld layers. one or

which is pictured het"e.
Distances in pm.
tor
I
.......... .
840
17 T1> Chemistry a f the Halogeno a nd the Nable Gases
molecular iodine be haves as a Lewis acid towards the iodide ion (as it does to other
Lewis bases: see Chapter 9):
(17.43)
Similar reactions occur with other halogens, and every possible combination of
bromine. chlorine. and iodine exists under appropriate conditions in aqueous solution:
(17.44)
The participation of fluorine is less common. but several fluoride-con taining trihalide
ions have been isolated as crystalline salts (Table 17.3). The triiodide ion presents
exactly the same problem to classical bonding theory as does xenon difluoride. and
although the triiodide ion was discovered in 18 19. only eight years after the d iscovery
of iodine itself. chemists managed to live wi th this problem for almost a century and a
half without corning to grips with it. The explanation offered most often was that the
interaction was electrostatic-an ion-induced dipole interaction. The existence of
symmetrical triiodide ions as well as unsymmetrical triiodide ions makes this interpretation suspect, and the existence of ions such as BrF; and IF;; makes it untenable .
Two points of view are applicable to these species. as they also are to the
noble gas fluorides: (I) a valence bond approach with promotio n of
electrons to d orbitals; and (2) three-center. four-electron bonds. The same arguments.
pro and con. apply as given previously. so they will not be repeated here. Independent
of the alternative approaches via VB or MO theory. all are agreed that Madelung
energy ("ionic character") is very important in stabilizing bolh the polyhalide ions and
the polyhalogcns.n
The polyhalide ions may conveniently be classified into two groups (Xj -type ions
belong to both groups): (I) those that are isoelectronic with noble gas compounds and
Tabt. 17.3
Palyhalogeft anions in
solh
Xi
1l
I:BrJ!CJIBr}
Jet;
IF}
IBrCI1Brr
Br)
Br1 CIBrCt;
Brfl
a; .
af2
1'7
x:I z-
x;;
Br,z-
.a-
16 BrIF;
I4 Br11 Brj
11Br1CI11 BrCI2
JBrCI)
JCJ,;
1a,F-
IF;
.t;
x:,z8-
Xi
,-'
x;
.- 9
I Fa
BrF6
CIF6
:l
t "
BrFi
CtF;
For cakulallons, see Wiebct1p. E. H.; Kndlt. 0 . /flt)'f. Cltmt. IH9, 8, 738.
Halogens in Positive OlOdolion States
841
have general formulas XY;. where n

an even number; (II) polyhalide ions. mostly
polyiodide ions. 1;. where .t can have various values. usually odd.
Group I polyhalide ions generally consist of a central atom surrounded by two.
four. six , or eight more electronegative atoms, with linear, square planar. distoned
octahedral, and square antiprismatic structures, respectively. These structures obey
the VSEPR rules and are closely related to polyhalogen structures. differing by a lone
pair in place of a bonding pair. They obey the rules discussed above for polyhalogeo
and noble gas compounds. The Group II polyhalide ions present some unusual
bonding situations, and so it is simplest to stan with I. and the two limiting structures
of the I) ion. The bond length in the iodine moleculeis 267 pm. We can imagine that
upon the approach of an 1- anion, the charge cloud of the 12 molecule will distort with
a resulting induced dipole. The greater the distortion of the iodine charge cloud, the
weaker the original I - I covalent bond is apt to become,28 and we might expect that
bond to lengthen somewhat. This is the siluation in ammonium triiodide: The 1-1
bond lengths are 282 pm anti 310 pm. The "intmmolecular" bond (original diiodine
bond) has lengthened by 15 pm. while lhe long "intermolecular'' bond is 40 pm longer
than a "normal" covalent bond and only about 80-100 pm shorter than a simple van
der Waals contact. Further approach by the iodide ion eventually will result in a
symmetrical triiodide system. Such is found in tetraphenylarsonium triiodide.
Ph4 Asr;. in which the two bond lengths are equal at 290 pm (Fig. 17.7).29 The
question as to why both symmetrical and unsymmetrical triiodide ions are found in
crystal structures has not been completely resolved. In many ways it parallels the
hydrogen bonding
(F-H-Fr
problem of symmetrical and
01 J IO
6
I
cb
cb
Jbl
1<1
67
,.
II
: !90
> !67
I .:90
edt
fig. 17.7 Structural chances as nn iodine molecule, 12 (a), is "flPronched by an iodide ion
and changes to an unSymmetrical (c) or symmetrical (d) triiodide ion. Distances in pm.
(b)
the unperturbed I - I molecule repre.seats the minimum in Jhe energy CU"'e ror 11\osc lv.o
otoms, any change in the 1-1 bond lolglh in the molecule mu.st resiAJ in a
in the origiNII
t-1 ponionofthebondenergy. lnotherwords, if a change in bond lc:nglh in 1-t cotldstrensJhen
Jhut bond, it would'"'""
occuutd without tht
the iodide ion.
2tl Since
or
"See Popov, A. I. Hu/ogtn Clttm. 196'1, I, 225; Wiebcnp. E. H. ;
E. E .; Boswijk. K. H.
A.dv. lnoq. Clotm. Rtzdloclwm. I HI, J, tl3-t69, for the original references and runher discussion.
842
17 The Chemisr.y of the Holagens and the Noble Gases
versus [F H- Fr (Chaplet" 8). We might equate the symmetrical arrangement with

optimal, very strong bonding. Indeed. in hydrogen bonding systems only the very
strongest. F- H- F and 0 - H - 0 (and not all of them). exhibit the symmetrical
structure. The unsymmetrical structure could be attributed to the polarization effects
from cations that may produce an imbalance in the triiodide system and make the
more stable.
unsymmetrical
The higher polyiodides provide a more complicated picture than the triiodide. The
pentaiodide ion, I;. is an L-shaped molecule which may be considered to be two
iodine molecules coordinated to a single iodide ion. Alternatively. it can be considered
to be two unsymmelricaltriiodide ions sharing a common iodine atom. There are two
bond lengths. 1.2 and 4.5 (282 pm) and 2,3 and 3.4 (317 pm). which correspond very
well to the bond lengths in the unsymrnetricallriiodide (Fig. 17.8a).
The .. tetraiodide ion .. as found in Csi4 has been found to be dimeric.
It
consists of anothet" leg added to the I5 ion to form a Z arrangement. II can be
considered to be a central I 2 molecule with an asymmetric.a ltriiodide coordinated to
each end. The ..short .. bonds of the triiodide groups (bonds 1.2 and 7.8) are 285 pm
and the .. long" bonds (2,3 and 6.7) are 300 pm. in fair agreement with the preceding
values. The bonds joining these triiodide moieties to the central diioJine .. molecule ..
(3.4 and .S.6) are longer than any encountered thus far: 342 pm (Fig. 17.8b).
The so-called heptaiodide ion is found in (Et4 N)I 7 No discrete I7 ions are
present. The structure is an infinite three-dimensional framework of tJiiodine molecules.. (274 pm) and symmetrical .. triiodide ions"' (290 pm) coordinated through .. very
long bonds (344 pm). A discrete 17 ion,alsoconsistingofone I) and two I! units. has
recently been characterized in (Ph4 P)I 7 (Fig. 17.8c)..l()
Finally. the enneaiodide ion. I9. is a still more complex structure. which has been
characterized as I7 + 12 or I; + 21!. but is probably best considered as a three-
Ii-.
II
tbl
(<I
Fig. 17.8 Structures ol poly;odidc ions: (a) The pcnt3io<lide ion. 1;; (b) the octaioditle ion.
(c) 1he heptaiodide ion as foond in f'h.Pt,. Solid lines represent csseminlly noriTllll
covalent bonds. dnshed lines reprelienl weakened or p:111ial bonds. and durt<:tl lines represent
very long and weak intei':ICJions. Oislllnces in pm.
10
Poli. R.; Gordon. J . C.; Khanna.. R. K.: Funwick. P. E. lno'll
- - -- -
--
1992. J/. l i6S-ll67.
Halogens ;., Pooiti" Oxidotion Sta-
843
dimen sional structure! similar to the so-called heplaiodic.le bu t or more irregular structure: with bond lengths or 267, 290, 318. 324, 343, and 349 pm. Unless the IaUer is
arbitrarily considered too long to be a true bond. the system must be con sidered to be
an infinite polymer. A portion
the struc ture is shown in Fig. 17.9 .
or
Fluorine-Oxygen
Chemistry
There is no evidence that fluorine ever exists in a positive oxidation state. This is
reasonable in view or the fact that there is no element thai is mort! electronegative and
capable of taking electron density away from it)l Certainly the oxygen compounds or
fluorine come the closest to achieving a positive charge on fluorine, and since their
chemisrry is in some ways comparable lo I hal of the other oxyhalogen compounds it is
convenient to include these compounds here.
Few oxygen nuorides are known. The most s table of these is oxygen difluoride. II
is usually prepared by the passage of fluorine through aqueous alkali:
(17.45)
or
Thermodynamically OF: is a slightly stronger oxidizing agent than mixtures oxygen

and fluorine. Thus. it occupies the extreme position in the standard electrode potential
table (Appendilt f), though this potential may not ulways be realized as a lternative
reductive pathways are available. It is relatively unreactive unless activated by an
electric discharge or similar high-energy source. In contrast to most molecules coot:lining fluorine. it has a very small dipole moment and thus has one of the lowest
boiling points)! of any inurganic cC)I!Ipounc.l. 49 K . Other oxygen fluorides have been
of which only O:F: has been w.:ll ch:u-u<:tcriz.ec.l . It is an orange-yellow solid
Fig. 17.9 A poniun or

the structure
or the
..cnncwooi<lc .. ion roond in

M c.N t,.. Tllc shortest
between this
moic1y and the next is only

J4'J pm.
" or coorse since dcctronq;utivity .. a 1\Jncri<>n
l ''h)'bridizatiun .. and "chlltgt"), it is

in a porticulo!T valence
!han
And. or course. >incc Ihe <liscinction bcl..-een loss
of .:l<etnlOIS and S"in in decuon.< twhich m.1y he two
.:lencc lllale< in the admiucdly hicJUy
clccm.,._.,,hvc nuble "'"'"'' " 1101
m:.dc. then: i.< 'llmL, t >kitmisho111n the liJcr:llwe over
nul impoll\lblc: I bot nuurinc miGht
laic lholl
w- meli'C
&nd itsdr in 8 COITiplUnd Wllh an dement
nuonnc.
thos.
The: tlipolc morntnl ui'OF, is only d.9'11 " tn-'" c m cD.:!'/7 Dl. Tlli
the
Ill' the
or I he hybritlized ox )'len an<l unhytnliud Ooorinc and the dl'ect ol tone
poit mnmcnJS. Simil:v molecule< nrc NF,. ,. 0.7Kl " to- C m (0.2lS 01. bp ISl K;
ris-FN=NF. p 3 O.Sl >< Ill_,. C m 1ll. lfl OJ. hr> lfi7.S K. Dipole morncn& values are from
Ncls<ln. R. 0 .. Jr.; tide.(). R. . h .: MIUYOII. A. A. S<ltnl Vul11ts ofEJ,rtric Dipdr
Mokcuks in the Gcu P#u;sr: !IISRDS-NBS 10.
DC. 1967.
J44
17 The O.mistry of the Halogens and the Noble Gose
that decomposes slowly even at low temper.Uures and is a powerful

agent.
Lillie is known of o.F2 which supposedly forms ns a red-brown solid at 77 K but
decomposes on warming.
Several workers have investigated the possibility of synthesizing lluorine oxygen
acids such as HOF. HOFO. HOF02 or HOF0 3 Despite the various claims to have
formed species such as these, it is the present opinion that only one. HOF, has been
synthesized. and it is also the only hypohalous acid that has been prepared pure.ll It
may be prepared by passing dilluorine over ice (fig. 17. 10):
( 17.46)
It is difficult to prepare and isolate because of its reactivity towards both water and
diftuorine (fig. 17. II):
HOF
+ H1 0
HOF
+ F1
---+
---+
HF + H 1 0
HF
(17.47)
+ OF1
(17.48)
Other compounds containing the - OF group are known: CF30F, 0 2NOF.

F_sSOF, 0 3CIOF. CH3C(O)OF, and CH 30F. These are all thermudynamically unstable compounds with strong oxidizing propenies, though some such as CF30 F and
F5 SOF are sufficienUy inert kinetically that they can be stored in cylinders.
Fig. 17.10 AJll>'l(atus for carrying CMJt the

of fluorine with cold ice. All p311s arc
made from KciF. Teflon, Vitcn plastics, or Monel metul. Rc:uction tube B is p;ac:ked with
that is frozen
Raschig rings cut from Teflon spaghetti tubing. and wet with 1-2 mL
with dry icc. Traps C and E are filled with dry Tcllon Rasehi& rings. Tube A is held at
-t96 c with liquid nitrogen, traps 8 und C :u -40 and - so c. respectively, with chilled
E and F ut - 183 c with liquid oxygen.
ethunol. trap D at -78 c with dry icc:. und
Gases are re-circulated with pump G. Ttle pressur-e is meusured with gauge I. and vacuum
pumps and a fluorine cylinder are auachcd throuah vlve J. The HOF collects in Tube E; the
OF: in Tube A. (From Appelman, E. H.; Juchc. A. W. J . Am. Chrnr. Soc. 1981, /09,
t754-17S7. Reproduced With pcrmission.J
n Appelman. E. H.; Jac:hc, A. W. J. Am. Clrtm. Sue. 1987, 109. 1754-1757. Pol. W.; l':lwelkc, G.;
Mootz. 0.; Appelman, E. H.
Chrm. In/. Ed. U.,t. 1988, 27. 39'2- )9l.
Halogens in Positive Oxidation Stoles
845
Fig. 17.11 Effect o(

rencJion tempo:rature on
yH:Ids of variou. products
from Ill<: reaction o( F, with
ice. (From Appclllllln,
E. H.; Juche. A. W. J. Am.
Soc. 1987. 109.
with pennission.)
Oxyacids of the
Heavier Halogens
The series of acids HOCI. HOCIO. HOCI02 and HOCI03 (or HCIO.
HCI03
HCIO.J is well known. arising from the disproponionation of chlorine and related
reactions:
Cl
+ 2H1 <? -;u+ HOCI + H 1 0 + CI-
(17.49)
CI2
+ HCO)
+ COz +a-
{17.50)
JO! + WW ---.;;- CIOj + SCI- +
(17. 51)
4KCI03
HOCI
.......,. ,_.,._
JKC104
+ KCI
(17.52)
.,.._IOO'C
Chlorous acid and chlorite salts cannot be formed in this way but must be formed
indirectly from chlorine dioxide which in tum is formed from chlorales:
KCI03
...:
: ".....
'
K2C 20 4
Cl01
(17.53)
In basic solution chlorine dioxide disprOponionates with the formation of chlorate and
chlorite, and the latter is used to form the free acid:
2CI0 2
+ 20H -
--+
Ba(CI01 h + H 2S04
CIO} + CIO)
___...
+ H1 0
2HOCIO + BaS04
( 17.54)
(17.55)
The heavier halogens fonn similar series of compounds although Jess complete. In all
probability neither HOBrO or HOIO exists. The periodate ion exhibits a higher
846
17 The Chemistry of the Halogens and the Noble Goses
coordination numberl4 (resulting from the increase in radius of iodine over chlorine) of
six. 10!-. as well as four. IO.j. For many years it proved to be impossible to
synthesize the perbromate ion or perbromic acid. The apparent nonexistence of
perbromate coincided with decreased stability of Olher elements of the first long
period in their maximum oxidation states. This reluctance to exhibit maximum valence
has been correlated with promotion energies and with stabilization through '1T bonding
(see Chapter 18). The first synthesis of perbromate resulted from the in situ production
of bromine by tr decay (compare to the synthesis of XeCJ4 above). It was soon found
that it could be readily synthesized by chemical means:
NaBr03
+ XeF1 + H 1 0--+ NaBr04 + 2HF + Xef
(17.56)
a good example of the use of noble gas compounds as oxidizing agents. They
are extraordinarily .. clean,.. providing a convenient source of fluorine with only the
.. inert" xenon given off as a gas.
A more practical synthesis of perbromate is to usc fluorine directly as the oxidiz
ing agent:
NaBr03
+ F 2 + 2Na0H--+ NaBr04 + 2NaF + H 2 0
(17.57)
Once formed, perbromate is reasonably stable. Aflhough perbromate is a

oxidizing agent than either perchlorate or periodate, the difference is nOI great:
00)
C!Oi
BrO.j
!O;
(17.58)
BrO)
Ul90 .
(17.59)
10]
(17.60)
The crystal structure of pOiassium perbromate has been determined, and it was
found that the perbromate ion is tetrahedral as expected from the isoelectronic CIO;,
IO,j', and Xe04 species.
Halogen Oxides and

Oxyfluorides
The heavier halogens form a large number of oxides and oxylluorides (Table 17.4).
Most nre rather strong oxidizing agents and some are extremely unstable. These wil!
Tobie 17.4
Halogen oxides ond
oxyfluorides
a.o
Br.O
CI1o.
Br1 0 4
Br30 8?
002F
Br02F
CIO,F
CIO!F3
Br03F
CIOl
CIOF3
BrOz
110 4
1.09?
120,
102 F
IOF3
103 F
102 F1
!OF,
,.. The chemiatry of the: onhopcrio<l:ue ion ;, m<n cumplicotc:d th:ln implied by the: rormut:J
Pcrio<lic acid often behaves a. adibuic uci<l rormina saltsorH,tO!-. Funhermore. pyro-type!Wlts
ate known wilh !be IOh oclallcclr.l shalinll edge$ and faces. Sec Wc:lls. A. F.
Cl,mutry,lth cd: Oxford Universily: London. 1984; pp 405-406.
.
--
--
Halagens in Positiw Oxidarian States
847
not be discussed here exce pt to call lll tention to the use of chlorine dioxide above
(Eqs. 17.54 and 17.55) and to its use commercially as a bleaching aaent. One exception
to the general reactivity of this class of compounds is perchloryl fluoride. G01 F.
Although it is inherently a strong oxidizing asent. it behaves as such only 31 elevllled
temperatures. It has a dipole moment of 0 .077 x 10- 30 C m (0.023 D), lower than any
o ther polar substance. Perbromyl and periodyl nuorides are also known and share the
lessened reactivity and low dipole moment but are somewhat less stable.
Halagen Catians
In addition to the polyhalide ions discussed previously, which were all unionic. there
are comparable cationic species known,).S although they have been studied considerably less. Many pure interhalogen compounds are thought to undergo autoioniZlltion
(see Chapter 10) with the formation of appropriate cationic spec.i es:
2101 =::: ICI!

2IF5 ;::
+ ICt;
(17.61)
tF; + IF;
(17.62)
In many cases these cationic species have

postulated on the basis of chemical
intuition Q)Upled with the knowle.lge that the pure interhalogen compounds are
slightly conducting (see Problem 17AI. Hom001omic halogen
can be prepared
in highly acid media. For example when iO<line i5 dbsolved in 60"/. oleum (SOJ
it is oxidized cby
S01 present) to yield a deep blue species. Conductomelric, spectrophotometric. cryol>Copic. and =cnetic
measurements
are all complllible with
stoichiornclric amount.s of oxidizin{! agents [such as
bis(lluorosulfuryl)peroxide or
pcntuHuoridel allow vnrious polyiO<line cations
to be prepared:
21 2
+ FS0200S02 F
2FSO)
(17.63)
312
+ FSO:OOS02 F
:!t; + :!FSO)
(17.6-1)
512 + FSO:OOSO:F
21 2 + 3AsF5
31 2
+ 3Asf5
51: + 3AsF5
:!I; + :!FSO.)
(17.65)
+ AsF,
.,. :!AsF; + :\ sF,
( 17.66)
+
-::
:!I ; + :!AsF
+ AsF)
(17.67)
(17.68)
The use ortiquid sulfurdioxic.le as solv.:nt

the
hcxfluoroarsenate salts of these cut ions including the very interesting tctraiodinc dication.
T he latter forms through dimcrization of
as its bright blue solutions are chilled.
DimeriZlltion is accompanied by a color ch;nge to red.
Although the presence of the m011:1tomic Clllion, I+. has not been c.lemonstrated in
the systems discussed above, there are conditions under which it is stabilized through
coordination and is well characterized. The dichloroiodatc(l) anion. ICI! . a simple
example. Other complexes or I may be prepurcd , as through the c.lisproportionation
of iodine in the presence of pyridine:
(17.69)
l>
See Gakspic. R. J.; l'asslncn, J. Adtl. I ""'f. Cl..,, Rodio<lonn. 1975.

BMJing (Dnlin) 1979, J7, 141-210.
Shovnir. J. SttVCr.
848
17Th Che,.istry af the Halagens and the Nable Ga..
Table 17.5
Polyhal"'l" catians
x;
x;
x:
a;
Br;
I+
)
c1: ""* _
11..
x; x; xv;
Br ...
$
7
, ...s 1..?
aF
BrF}
IFj
tc1
IBr}
x2r
Cl2f+
12a
11 Br+
XYt
XYt
OFt
BrF;
CtF;
BrF;
1Ft
IF:
Brra
This brief overview has not included all of the polyhalogen cations known. but merely
discussed a few typical examples. See Table I7 .S for a listing.
Ha lides
Although many of the compounds of the halogens discussed thus far have exhibited a
halogen in a positive oxidation state, most of the chemistry of this family involves
either halide ions or covalent molecules in which the halogen is the most electronegative atom.
Physical Inorganic
The pertinent trends in the Group VIlA (17) elements are size and tendency to altract
electrons (Table 17.6). IJ is only when both these factors are considered that the
chemistry of these elements can be rationalized. The most obvious trend in the family
is the
for electrons. "The ioniwion energy decreases from fluorine to iodine
as expec ted. There is an apparent anotn:lly in the case of the electron affinity of
fluorine, which is lower than that of chlorine. The small size of the fluorine atom
causes it to be saturated quickly wi th electron density, and the addition of a unit
c harge causes some destabilization (see Chapte.r 2). The great electronegativity of
fluorine combined with its small size (which enhances Madelung energy from
s + s- -r effects) results in a much greater exochermici ty of reactions of fluorine than
those of the remaining halogens. In covalent molecules it is exhibited by compounds
of fluorine without ocher halogen analogues, for example, AsF$, XeFu and IF7 In
aqueous solution it is exhibited by the high emf of the fluorine electrode resulting from
large hydration energy of the small fluoride ion.lf> This much greater reactivity or
fluorine has led to its characterization as a "superhalogen.
Chemistry of the
Ha logens
Table 17.6
Rodii, ionization nllr9J,
elec!Ton atronity, and
elec:tronetativity of the
halog-
,. Allcmali.-dy 11\e electrode polcnliaf CDII be a>Cribcd to case with wtkh lht F - F bolld is broken.
AI shown by lllc (dlowi!W discussion lht inlcrmalicn
bond cncrll)'. size, eltttroncpvity
cnc'l:Y. etc is coqllex and allributint evct")'llliq to OftC faciO< Is unwise.
Haliclea
The
Anomaly
of Auorine
849
Quite often the first member of a periodic group differs from the remaining members d
the group (see Chapter 18). In the case of fluorine the anomaly is quile pronounced.
Polilzerl7 has illuminaled this odd behavior by documenting the weakening of bonding
by fluorine to other elements compared with tha t expec ted on the basis of extrapolations from the heavier halogens. For example, we have seen I hal the electron affinity
of fluorine is less than might have been expected from the trend of the Olher halogens .
U this trend is extrapolated to fluccine, a value
kJ mol- 1 is obtained, 110 kJ
mol- 1 grealer than the experimental values. As a resu lt of the lower electron affinity,
ionic compounds of fluorine have bond energies which are slightly more than 100 kJ
mot- weaker than values extrapolated from the other halides: LiF (104 kJ mol- t
lower), NaF (108 kJ mol- 1 lower), KF (117 kJ mot- lower). RbF (104 kJ mol- 1
lower). and CsF (130 kJ mol- 1 lower). This d estabilization can be attributed to forcing
a full (or nearly full) electronic charge onto the small fluorine atom. The surprising fact
pointed out by Politzer is thai covalent compounds of fluorine seem to show the same
destabilization. In Fig. 17.12 the dissociation energies of the hydrogen halides and d
the C - X bonds in the methyl halides are plotted against the reciprocals of their bond
lengths . The compounds of the three heavier halogens fuU on a straight line which.
when extrapolated. predicts values for the fluorine compound that are 113 kJ mol- 1
(HF) and 96 kJ mot- (CH,F) too high. This indicates thai even when sharing an
electron from another atom fluorine is destabilized by its small size. Finally, the
fluorine molecule itself has a notoriously weak bond ( 155 kJ mol- 1) compared with
chlorine (243 kJ mol- 1), and it is some 226 kJ mol- 1 ( 2 x 113) weaker than the
extrapolated value . The weak bond in
has traditionally been interpreted in terms d
lone-pair repulsions between the adjacent fluorine atoms . There may be a more
general phenomenon in terms of small size. charge capacity,
electron-electron
re.pulsion.
Mg. 17.12 Bond

dissociation enersies and
bond lengths of the

hydrogen halides. methyl
halides. ancl halogen
molecules. Nooe that this
figure. which is taken
dln:ctly from Politzer's
work. ponrays in a
different way relationships
that are closely related to
Fig. 9.7. (From Politzer. P.
J. Am.
Soc. 1969,
91. 6235. Reproduced with
permission.I
J1
Politzer, P. lnoTt(. Clrnn. 1m. 16. ll$0.

P. In HmnnutomJc Rings. Chains und Muc
romolf:t-ul<s ofMain CAoup Elrmtni; Rhcinaold. A. L., Ed.; Elsevier: New York. t9n: pp9S-t tS.
See also Politzer. P. ; Huheey,J. E.; Murray.J. S.;GrodzX:ki, M. J . Mol.
1991, 2.l9, 99-120.
850
17 The Chemiatry af the Halagena aftd the Noble Gases
So how do we resolve this apparent paradox: Is fluorine a "superhalogen" or a

''subhalogen"? Does it bond beller than the other halogens or worse than expected?
There really is no conflict here: it depends upon what one is using for a reference. In
comparison with the heavier halogens. fluorine is by far the most active. the most
electronegative, and pr-ovides the most strongly exothermic reactions. In this regard
the weakening present in any X- F bond is offset by the weak F- F bond. so the
overall enthalpy of the reaction is not affected. and the effect of a high eleclronegativity on Madelung energy and electronegativily energy terms is dominant .
Fluorine has three factors favoring it over the larger halogens, all resulting from its
small size: (I) the largest electronegativily, a t least for small partial charges: (2) large
Made lung energies in polar molecules; and (3) good covalent bonding resulting from
the ability lo "get in close" to the a<ijacenl alom.l Except for F1 in which factors I
and 2 cannot come into play. fluorine typically forms slronge.r bonds than chlorine:
H- F = 56S, H-CI = 428: Li- F 573. Li-CI 464;C- F 485.C- CJ "'
327 (in kJ mol- 1). Thus fluorine displays all the properties el(pected or lhe smallest
haloge.n . The deficit of about 100 kJ mol- 1 is simply an example of the law of
diminishing returns: AI some point decreasing site no longer provides increasing
bonding benefits in proportion tofonhu dtcrau in sitt. Were il not for the saturation effect coming into play, fluorine would probably be a "super-superhalogen"!
A very similar question thai depends entirely upon what one takes as "normal" or
standard is the question of the covalent radius of fluorine. One half of the single
2 71 pm (and so listed in Table 8. 1).
.:ovalem bood length in dilluorine is 143 pm
One can then employ the Schornaker- Stevenson relationship and auribule the shortening land strengthening) of an M- F bond to ioniccovalent resonance (Madelung
energy) and account for the fact thai the M - F bond is always shorte r than 'Moo- +
Alternatively, once can assume thallhe bonding in most fluorine compounds is
" normal" and thai the long (and weak) difluorine bond is the "anomaly" because o(
the lone pair-lone pair repulsions. The two viewpoints are essentially equivalent. For
a careful analysis o( the covalent bond radius o( fluorine, see Gillespie and
Robinson)v
Because of its supreme n:activily. the preparation of elemenl nl difluorine was not
accomplished until long after the prepar.>lion o( the other halosens ...., So most 'hem'"ccpted the im!)Ol;sibility of producing diftuorine in any pr:tctical way other than
the dccrrolysis of anhydrous HF:
''-
(17.711)
However. Christe.. has shown that by taking advantuse oft he dilference in stability of
a given oxidation slate of a transition metal depending upon whethe r it is fully
"' Nutc thut with

cxcc:ption d hydroacn. Ouorine i tltc lmlllest bontli"'! atom known. arwJ \0
<llmo.\1 every t>ond il make wil be with u bt"'r atom.
W Gillespie. R. J .; Robinson. E. A. IMfl!. Chrtn. 1992. Jl. 1966-1%).
.. Foran interatingreviewdthcHIIy hislorydl\uorinl:chcmi>lry. '< Flwrittr: TM FirJtl/undrrd
Ynm 11886-1986); Bank&. R. E.: Slwp. 0 . W. A. ; Tutluw. J. C . F.d. :
New
Yurt. 1986.
ClvisiC. K. 0 .
Clrrm. l916.1J. lnt- ln2. .SC.: al&o Qlriste. K. 0 .; Wohon. R. 0 . /""'71.
Cl.-m. 1917. 16. 2S.S4-2.5.56
--- -- --
Halides
851
can be gener.lled chemically. Potassium hexcoordinated or not, difluorine

afluoromanganate(IV) can be prepared by reduction of potassium per maoganate:
2KMn04 + 2KF
+ JOHF +
... HF
2K2MnF6 l + 8H20 + 30: (1 7.71)
Allhough
6 is stable (perhaps because of ils insolubility), the free Lewis acid
Mnf4 is not. Preparation of the Iauer is accomplished by using very s1rong Lewis
acids such as SbF,. TIF4 , and Bifs (see Chapter 9) which are also redox stable in the
of diftuorine gas.
(17.72)
Similar reactions can be run using nickel or copper as the transition metal.
Whatever one's interpretation of fluorine chemistry. sub-. super-. or super-superhalogen, it is obvious that the thermochemistry is extremely important to the understanding the chemistry of fluorine. II is fortunate that good. lhorouh thermodynamic
data on fluorine compounds are
Astatine
or
It was noted above that discussion

aSI:Itine loge.t her with the Olher halogens is
inconvenient. AUhough it is, as expected. the most "melallic" the halogens, there
are few values or experimental data to cite in support this. (Note for example thai
such fundamental quanti1ies as experimental ioniz:ltion energies are unavailable.)
Various isOiopes asl:ltine are produced only in trace amounts, with half-lives of a
few hours or less. and 1herefore the chemistry a:sbtine is essentially the descriptive
chemistry obtained by tracer methods:
amounts are not available. The
best known oxidation stale of astatine is - 1. Astatine may be readily reduced to
aslatidc:
or
or
or
(17.73)
which forms 11n insoluble silver astutide precipitating quuntilatively with silver iodide
as carrier.
St udies elemenml
are complicated by the
small amounts of
"staline
are rc,lllily aua.:k.:d by impurities that normnlly would not be considered important. Most studies of AUOI involve an excess of iodin.: which ties 1he
"statinc up in All molecules ..., II behaves much as micht be
from the known
h.:havior
1!: It readily extractable into CCI. or CHCI, and may be oxidized 10
positive oxid:uion states by reasonably mild oxidizinc acenls.
The best ch:1r.1cterized positive oxidation stale is At(V). As1a1a1e ions may be
formed by oxid;llion of At by pc:roxodisulfutc, the eerie ion. o r pcriooalo::
or
or
AI-+ 6CeH
+ 3H 1 0--+ AtO) + 6Cel+ + 6H
(17.7-1)
As such it may be quantitatively precipitated with insoluble iodato:s

as
and Ba(IO,lz
It appears that pel'llSt:Jt:Jte. AtO.j. has not been prepared. When astatatc W"dS
treated with very
oxidizing
a negligible amount the activity precipi-
or
Radillr111. 19111. U . I-SS.

...Win:: in All .houkl be COI>l<iolcn:d All II inslc:kl of AUO)
since :Walinc
less dcelronqattvc lhun iolliolc. The: dill'crcnce in
is
certain 10 be very Sl11311. ho__.. and All aon llfobably bat be considcrcd as n alrnosl nonpolar
mo1cat1e wilh csseNioly uro ch:ltae on bolh UIOIIIII. bdluWI8 like i}.
"Wooll. A. A. AJI,. IIIMJI.

4>
Slriclly
mi@hl "'11"'
852
17 The Chemistry of the Halogens and the Noble Gases
tated with Kl04 , most precipitating instead with Ba(l03 h. The apparent absence of
At(VII) is surprising in view of the lower electronegativily and larger size of astatine.
If peraslatic acid does exist. it is probably with coordination number 6: H,At06
At least one more oxidation state. presumably At(l) or At(lll), is known in
aqueous solution, but it has not been well characterized. It can be produced by
reduction of astatate by chloride ion qr oxidation of At(O) by Fe3 +. Little is known
about it except that il differs from the other oxidation stales of astatine. (I does not
precipitate with silver (AC) or barium (A tO;). nor extract into CCI4 (At!), but it doe:r
follow the dipyridineiodine(l) cation.
Pseudohalagens
There are certain inorganic radicals which have the properties of existing either as
monomeric anions or as neutral dimers. In many ways these groups display properties
analogous to single halogen atoms, and hence the terms pseudohalogen or halogenoid
have been applied to them. Examples of pseudohalogen behavior may be found in the
chemistry of cyanide, thiocyanate, and azide anions. Some typical reactions are:
I. Oxidation o x- ions to form dipseudohalogens:
2SCN-
+ 4H+ + Mn01
(SCN}1
+ 2H1 0 + Mnl+
{17.75)
2. Oisproportionation of the free pseudohalogen by a base:
+ 20H-
- > CN-
+ OCN- + H 20
(17.76)
3. Precipitation by certain merol ions:

Ag+
+ N3 ___.
AgN3l
(17.77)
4. Formation of complex ions:
a,!+ + 4SCN- -
[Zn(SCN)4] 2-
(17.78)
5. Formation ofacids with hydrogen, HX. These acids generally are considerably
weaker than the hydrohalic acids, e.g., pK. for HCN "' 9.
The extent to which the various pseudohalogens resemble halosens is generally
quite high. with some remarkable parallels:
c.t+ !12 + Cull

+eli+- i(CN)2 +
21- +
2CN-
(17.79)
{17.80)
ahhough, however, there are several exceptions. Thus thiocyanogen, (SCNh is

stable only at low temperatures, and at room temperature polymerizes to (SCN)_...
With respect to division into hard and soft species, most pseudohalogens are composed of several nonmetal atoms, often with multiple bonding, and so are quite
polarizable. As such they lend to resemble iodine considerably more than fluorine.
Some are ambidentate, however, and can behave us reasonably hard bases by coordination via a nitrogen or oxygen atom (see Chapter 12). FinaUy, pseudohalogens can be
compared with the halogens on the basis of their relative oxidizing power. They tend
to resemble iodine and bromine (see below for the values of these elements):44
.. Oara rrom Bard. A. J.; Pnrsons, R.; Jordan, J. Standurd
Dekker. New Yorlt. 198S
---- --
In Aqurous Solution; Marcel
EledrachemKiry al the HalogenS and Pseudohalagens
(CN)1
+ 2H+ + 2c- -----+ 2HCN
(SCN}1
+ 2e-
f!J 0.37S V
f!J -
-----+ 2SCW
853
(17.81)
o.n v
(17.82)
In summary, the concept cl pseudohalogens proves useful in systematizing the

chemistry of some of these nonmetallic s roups, but it should never be followed
blindly.
Electroch.mislry
of lhe
Halogens and
Pseudohalogens
Simple Lat imer diagrams for the halogens are given bdow. The data are from
Bratsch ..U
Acid solllllon:
o.m
1. 1)1
uu
Ll ..
I.: I
Basic solution:
oo;
Cl01
......
BrO"
oo;
nr
Cl2
0.11'10
Br1
O.lo.
., Brahclo, S. G. J. 1'111$.
ClO"
R4 Dolo J.M. II, t-21.
Br-
Cl"
854
1 7 The Chemistry of the Halogens and the Nable Gases
Problems
less thnn that of
17. 1. Consi<krlhc fonnntion ofO; tptFJ-. Why is !he ionizalioncnCJ'liY

0? Is it likely that a compound N;[PtF6 1- will form?
17.1. The absence of intcrnction between noble gases and the Lewis ucids BX, was demon
strotcd by Raman spectroscopy. DiSCUS$ the nature of the evillcncc and what would have
been observed if thue had been a signilicant interaction.
17.J . Show how the FHF- ion (Chnpter8) can be treated as a three-center. four-clecr.-on hond.
17.4. Suggestautoionization possibilities for BrF,. ICI, and BrF,. and probable stnJctures for
the ions formed.
17.s. Pure iodine is purple in color as are its wlutions in CCI4 and CHCI,. ond ben:tene.
Aqueous solutions of K I, are brown. Solutions of diiodine in neetone. dimethyi5Uifoxi<k.
and dicthyl ether are brown.
an explanation.
11 .6. Succest syntheses fot
a.
xca.
b.HQO,
c. KBr04
17.7. Suucst probable slr'Uctures for 14 0 - and 1a ;. and aive reasons why the two are
probably not isostructurol.
17.11. The production of pseudohalosens requires mild oxidi:ting conditions !Eq. 17.75). Why
do you suppose thot it has never been possible to oxillize the o:tillc ion to hexanitrogen
(d"'LYI)?
(17.8J)
17.9. Why ..rc the tr.aroaen cations Cl). Br). and I) best isolated as salts of AsF;:. SbF; . and
similar anions?
17. 10. The mdting points of the ftuorides MF. MF 2 and MF, are gcncrolly somewhat lower
th:sn those of the correspondina oxides. M20. MO. "h0 1 becauK of the c=ter laniee
c ncrsy rcsulli11 from the dinegat.ivc oxick ion. o"-. Yet ..11 of the following reactions are
cxothennic. Explain...
U:O + F2
MgO + F2
MsF2 + !0 2
fc:20 3 + 3F1
2FeF, + i0 2
Zr01 + 2F2 -
2Lif + 102
ZrF 4
+ 02
- 602 kJ mor-
(17.8.1)
(17.85)
1
= - 1162 kJ mul-
( 17.K6l
-740 kJ mot-
(17.87)
=
t.Glwn =
- 740 kJ mol -
17. 11. If you ask an oraanic chemist which

can form the l:ttJ:CSI number of compound<
lnOI that more than u fraction have been synthesi:tcd yet), you will osoully l)el one of 1wo
an<wcrs: c:arl>on from some. hydrogen from others. If you ask un inoraanic chemist. you
gd a third answer. Whal is your answer? Discuss.
17. 11.
it is Slated lhal xenon rorms bonds wi1h only 1he mOSI dc:ctroncgaJi,.,
clements such as the very adivc fluorine lind oxygen. How can you rcconciJ., lhis with
the furmation of the Xe-Xe bond in Xc;? (Hinl: Rethink Problem S.IS.)
On
I7.1J. Xc{ obviously will have a fairiy high electron affinily 1sce the
enerJ:Y of atomic
xenon). and if it gains n electron. it will dissoci:sle (see Chupter S). Combine these facts
with the choice of SbF, as solvent and
theory to provide a self-consistent
interpretation .
- - -- - --
.., Portier, J. Angw. Ch<'rrt. /nJ. Ed. EnR#. 11176. 15. 47S.
.
.. ..
.
Problems
855
17.14. The OSeF, and OTeF, groups are very electronegative as shown by the stability of their
xenon compounds. If y(lU did not do Problem 5.30 when you rcud that chapter. do so
now.
17.15. The photoelectron spectra of Xe. F,. XcF,, XcF OXeF4 and XeF6 arc shown ill Fig.
17. 13. What lrlormation c:tn you obtain from these spectra? (The appearance of two
pc3ks for Xe is attributable to the ejection of 3J electrons of difl'ercnr j values and is
irrelevant to the question being asked.)
17 .16. Consider the series of xenon oxyfluoridcs nnd their relative ncidity. Discuss the reasons
for the orckring of these C<Jmpounds. Cnn you semi-quantify your answer?
Kinetic: <norgy (eV)

810
80S
800
79S
790
78S
780
400
0
lOll
tOO
"It
1000
t;
600
c"
coo
400
Bintlina nx:rl)' (cV)
ng. 17.13
Phmoclcctron
of Xc. F,. XcF,. XcF OXcF nncl XeF . (From Carroll.
T. X.: Sh:1w. R. W.. Jr.; Thomas. T . D.; Kin.Sic. C .: Bartlett. N.J. Am.
Soc. 1974.
96. 1989. Reproduced with permission. I
856
17TM 0\emisfry of the Halogens and the Noble Gases
17.17. a. Predict lhe rnostlikely by-products of the reduction of

page 834.
to Xej as discussed on
b. Write balanced equations for all o( these reactions..

17.18. The xenon ftuoridcs are described in this chapter os both ftuoridators and fluorinators. Is
this a typographical error? Can these terms be diffcrentillted? Discuss.
17.19. On page 1127the statement is made thut " the electron affinity of positive helium, etc. is
greater than that or any uppropriute species X . .. " What Is the electron affinity
(numerical value) of He?
17.20. A general rule or molecular structure derived from VSEPR lheory and Bent's rule is that
lone pa;rs and substiluents
low elcctronepivity pnfer equatorial positions in a
trigonal bipyramid, wllereas substituents of hii!l eleclrone&alivity prefu axial positions.
T he pcntaftuoroxenate(IV) ion, XeF;. seems to reverse this rule by having the LPs
pn:fcremially oc:cupyil\llthe axial positions. Disalss.
or
17.21. On p3ge 832 the sw.emem is made tholl In "most fluorides the reduction of sleric factors
to the surface the molecule, . " and yet !here are two
allows the lone pa;r to
hexaftuoro species mcnlioned in this
that are perfectly oc:t.al1cdral What are
they'! How can they be octahedral in liahl or the above statement?
or
11.22. Allbough the Xc-0 bond (-80 kJ mol- 1) is not as strona as that in the xrnon fluorides
(-180 kJ mol- 1), it is far from bcina the weukest bond known. How then is it possible for
XeO, to be so viokntly cxolhcmic (expbivc) when it decomposes?
17.23. If you <lid not do Problem 14.15 when you read Chapter 14. do so now.
17.24. On page 834, the statement is made: " Hydrosen xenale ions dispropo11iona1e in alkaline
solution to yield perxenaaes . . , " Can you confirm this asse.rtion bosed on the Latimer
diagrams for xenon?
Chapter
18
Periodicity
T he most fascinating aspect of inorganic chemistry as well as its most difficult

problem is the dive.r sity of reactions and slt\lctures encountered in l.he chemistry of
somewhat over one hundred elemenls. The challenge is to be able to areal adequately
the chemistry cl bclnlnes and noble gas fluorides , lniiiSition metals and inner transition
metals, cuprate supemlnductors and zeolites, all without developing a srparale set cl
rules and theories for each element or system. Much of this book has been devoted to
establishing relationships that connect various aspects 0( inorganic chemistry. The
tool that the inorganic chemist uses to systematize elemental relationships is the
periodic table, now somewhat over one hundred years old. It is considered so
essential that no gener.ll chemistry textbook would be complete without a discussion
0( the trends summed up in Chapter 2. Unfonunately. the impression left by these
textbooks is often simply that all periodic propenies vary smoothly.
Fundament a l T rends
The basic trends of the periodic chan have been discussed in Chapler :!. They may be
summariud as follows. Wirhin a given
there are increases in size and decreases
in ioni7.ation energy. electron affinity. electroneg;ativity. etc.
the atomic
number a.:ross a given period resuhs.in con.:omitant incre:rses in ioni:w tion. elecaron
affinity. and elect ronegativity. but a decrc3se in size. The change in effective nuclear
charge within a period is re:asonably smooth. but the various periods differ in length (ll.
18. and 32 clements). The properties of an element will depend upon whether it follows
a n 8. 18, or 32 sequence. One of the best known examples is the very close similarity
in propenies of hafnium, tantalum. tungsten, and rhenium to those of zirconium.
niobium, molybdenum, and technetium, respectively. as a result of the lanthanide
contraction and associated effects. These anomalies continue through the elements
gold, mercury,thallium, and lead. Similar but smaller effects follow the filling of the 3d
orbitals (rarely referred to as the scandide" contraction).
Another area of the periodic chan revealing pronounced differences between
simii:J.r elements is between the first ten, H- Ne. and those immediately following,
I Pcrio<lic classilicali<>ns of the clcml:nts by
Omilri Menddccv :tlld by Loth:lr

For a crntcnniak:ddlt:llla dscuaion of the pdiodic table. S van Sprooscn, J. W.
Sy>trm o/Ciormk:al Elrmrms; Elsevier. Anwtenbn, t969.
in 111(,9.
Prriodic
857
858
18 Periodicity
Na-Ar. II is not canpletely obvious why this is true. Cerbinly the lighter elements
in their ground states, and therefore
utilize only the Is, 2s, and 2p atomic
simple bonding theory. whether VB or MO. suggests four covalent bonds. In contrast.
VB theory suggests that the presence of d orbitals in e.lements with 11 2:: 3 allows
hybrids with more than four bonding o rbitals. However. the use of J orbitals by
nonmetals presents energetic problems. is unnecessary in the simplest molecular
orbital approaches, and has been one of the most controversial topics in bonding
theory. Before entering this theoretical discussion. a brief examination of chemical
differences is appropriate.
First- and
Second-Row
Anomalies
In many ways the first ten elements differ considerably from the remaining 99.
Hydrogen is a classic example-it belongs neither with the alkali metals nor with the
halogens :llthough it has some properties in common with both. Thus it has a + I
oxidation state in common with the :llkali metals but the bare H+ has no chemical
existence! and hydrogen tends to form covalent bonds that have properties more
closely resembling those of Cllrbon than those of the :llkali metals. With the halogens it
shares the tendency to form a - 1 oxiW!tion state. even to the extent of forming the
hydride ion, H- ; however, the Iauer is a curious chemical species. In contrast to the
prOton which was anomalous because of its vanishil1ly small size. the hydride ion is
unusually large. II is larger than any of the halide ions except iodidc!l The sour.:e of
this apparent paradox lies in the lack of control of a single nuclear proton over two
nulually repelling electrons. Since the hydride ion is large and very polarizable it
ccnainly dues not extend the trend orr- throuch r of decreasins size and
basicity and hanlness.
Tbo: clements of the second row also differ from their heavier congeners. Uthium
Is anomalous among the :llkali metals and resembles magnesium more than its con!!Cr>ers. In tum, in Group IIA (2) beryllium is more closely akin to alu minum than to
the other alkaline earths. Tile source of this effect is discussed below. We have already
that fluorine has been termed a superhalogen on the: basis of its diff.:rences from
th.: r.:mainder of Group VIlA (171.
On.:
difference that the c:Jc:ments (j to F huve with resp1.-ct to their hea\'ier
couJ:Cn.:rs is in
flO"'cr. Thus lluurin.: is much mt1rc n:nctiv.: than
chlurine. bromine, or iodine; lithium
r.:activc than its congl!n.:rs. me must
.:lcctroncgative and smallest element or each fumily will he the tine: in 1h.:
rnw.
The great polarizing power of the Li cation was commented upon in Chapter 4.
As a result of its small size and higher cleclroncg:uivity this ion destabilizes salts that
are
for the remaining nlkali metals:
wlk disapprow of wrili"'l H)O ottc:n poin1 rut th:ll the hydrnlion number of 1hr H+ i
unrt:>in and "'all caliom .,.e hydr.ucd in solUtion." To I real H trulhcr thar> H ,o 1 os u euion
Otimilar to Na . tor curnplc. is 10 equate nuclenr
wilh :11oom. a
hy :t foetor uf
abouJ to>.
) Paulint:
o/tlw CMmK-ol B<111d. 3<11 e<l.: Cornell: llhloca. NY. 19110; p Sl41 ""- l'tO.;de<J
an csum:uc of !OK pm forlhc byUri.Jc;.,., .:omp;we<llo
I'"' tor I'. To he .urc. 1hc eai>lcncc ol'ar>
hydrid: ion is even leu likely th:ln u larp: unpllnme<l anoon of .arne llthcr kind. bul
insotJr :0.\ ionic r.Jdii have mc:onirls lhl' woui<J he Jhc he<t C<llrmle of !he 'li7.C of U(r.., hydride ion.
Tbe inhc:rcnl unn::JCiivU)' ollilfliwn is

"'lUW'A <OIUtion by Jllr C:Jt>Jhcnnic hydralion of the
YCrJ small u ion.
in aencr.ll.lilhium is 11 leu reactive rneJotth:ln Na, K. Rb. or u .
---- .-
Fint- and Secand-ltaw Anamaliet
+ H 10
( 18.1)
No reaction
(18.21
2liOH ;;;....: Li 2 0
2NaOH
;;;u;;;;:
2liSH ____. li1S + H1 S

Li10 + C0 2
Li1C03 -
859
(18.3)
( 18.4)
In contrast. fo r the large polarizable hydride ion which can bond more strongly by a
covalent bond the lithium compound is the most stable:
UH
-.;;;;;-+
2NaH
Size Effects in
Nonmetals
No reaction
(18.5)
Naz + H1
(18.6)
--;;;;;-+
One of the most obvious c.lilferences between the first ten elements anc.l their heavier
conge.n ers is in their mOJJtimum coordination number. usually (out or less in simple
covalent molecules (Table II!. I). Arguments of the radius rutio type suggest that these
a toms would have lower coordination numbers and that these stcric effects would be
relaxed for larger a toms. We have seen that this is true for coordination compounds of
tra nsition metals (Chapter 12). Table 18.1 can be readily interpreted in these terms:
The smallest :uoms have a maximum coordination numbe r or four.
atoms have
coordination number six. and only the largest have coordination numbers as h ish as
eight . In addition. the highest coordination numbe rs
with the small ftuorine
utoms as ligand ..< The hydroxy group. OH.
very similar in size. cltctroneg:lli\'ity.
and other bon<.ling
10 the Quorine atom. yet there :tre distinct differences
between the oxygen and fluorine compounds of t he nonmetals. The occurrence of
mulo:culcs with the maximum numlxr of hydroxy group$ tthe M><lled on ho acids) is
Even the relatively
ox)-gen atom tends to resul t in lowc:r coordination
numbers. Thus. in contra,tto the: ftuorides shown in Ta ble Ill. I. onhocaroonic acid.
C(0Hl4 and onhonitric acid. 0Nt0H}3 :1I"C unknown. the stmplc: adds of these
eleme nts being three-coordinate. Q-C(OH), and O,NOH .
The next two series or nonmetals. silicon through chlonnc and germanium
through krypton. \how 3 maximum coordination number of six in hexaOuoro a nioM.
SF,. and T.:F,.. Ev.:n her.: the
and oxyanions typicall y 'huw .a coordination
Table 18.1
Maximum coardinatian
numl>vs altl.e na-1 as

dlawn by the lluaridn
OFj
SF,.
FF (Fj')
elF:
IF7 (1Fi l
N. 0. alkl Olhcr clcmcnts can oehicvc

higtler coordination in onium .ults. e.a
NH;.
i advanla&CCIUS n<lt only fmm the

viewp<>inl bul also rrom the rnct !hal lhe rc:dox b<:hOviur
wcQ sultallo lilllbiti:t.c hi@)> o>lidation suuc:o. To put i1 another. bvl ,-quiv-lcnl.
High oxidation slllle
ore 1\otd
and the ftuoridc ion is the hlnlcsl possible b<lsc.
o( lklorinc
860
18 PeriodidiJ
number of four as in H3P04 , HCI04 , und HBr04 , and the silicates (see Chapters 16
and 17).
The l:lrgest nonmetals show coordination numbers as high as eight in the octaHuoroonions. IF; and XeFi- (see Chapter 17). The corresponding oxyacids and
oxyanions show a maximum coordination number or six: JSb(0H)6
Tef0H)6
OI(OH)s, and [Xe0J 4 - . Of these, apparmlly only iodine shows a maximum oxidmion
slate wilh a coordination number as low as four: Periodic acid can exist as either
OI(OH), or H104
r,
The Diagonal
Re lationship
II was mentioned previously that a strong resemblance oblains between Li and Mg. Be
and AI. C and P. and other "diagonal e.lements." and it was pointed ou t tha t this could
be related to a size-(:hurge phenomenon. Some examples of these resemblances are as
follows:
lithium-Magn.Uum
There is a large series of lithium alkyls and lithium aryls which are useful in organic
chemistry in much the same way as the magnesium Grignard reagents. Unlike Na. K.
Rb, or Cs, but like Mg. lithium reacts directly wilh nitrogen to form a nitride:
3Li1
+ N1
2Li3 N!
6Mg + 2N 1
2Mg,Nl
(18.7)
(18.8)
Finally, the solubilities of several lithium compounds more

resemble those or
lhe corresponding magnesium salts lhan of other alkali metal salts .
Berylliwn-Aiuminum
These two elements resemble each olher in several ways. The oxidation emfs of t he
elements are similar (t:0Bc c 1.85: E,!. 1 1.66), and althoUSh reaclion with acid is
thermodynamically favored , it is r.uher slow, especially if the surface is protected by
the oxide. The sim ilarity of the ionic potentials for the ions is remarkable ( Be2 48,
All+ = 56) and results in similar polarizing power and acillity of the cations. For
example. the carbonates are unstable. the hyd roxides dissolve rcallily in
base.
and the Lewis acidities of the hntilles ure oomparublc.
Boron-Silicon \
Boron differs from aluminum in showing almost no metallic propenies anll its resemblance to silicon is greater . Both bot-on and silicon form volatile. very reactive
hydrides: the hydride of aluminum is a polymeric solid. The halilles (except Bf,)
hydrolyze to form boric acid and silicic acid. The oxygen chemistry of the bo r.ates and
silicates also has certain resemblances.
Carbon--Phosphorus, Nitrogen--Sulfw, and Oygen- Chlorine
AU metallic properties have been lost in these elements. and so charge-to-size ratios
have little meaning. However. the same effects appear in the electroneg;Uivities of
these elements, which show a strong diaeonaJ ell'ect:6
1bc$e v:lll.les ere P:nllin thoo "'od""'liaal ettctroncplivitics l'lllhcr than lhooc lxlscd on ioniz.31io4
cno:ray-declron alli.-.y. This dloCe ol cmpiric:al v.duos was rrs6c 10 cbvi:Mc lhc nc$Sity or
c:l!oosinc (artilrarily) lhc proper valence siDle (h)'bricliulioftl.
-
The Use of p Orbitah in Pi landing
C = 2.SS, N = 3.04
= 1.90 ',,P = 2.19
Si
0 3.44,
861
F -3.98
S 2.S8 ' ', Cl - 3.16
The similarities in electronegativities are not so close as that of1he ionic po1entials for
and All . The heavier element in I he diagonal pair always has a lower electronegativity. but the effect is slill noticeable. Thus when considering elements that
resemble carbon, phosphorus is oflen as good a choice as silicon, and the resemblance
is sufficient to establish u base from which notable differences can be formulated.?
The Use of
p Orbitals in
Pi Bonding
Carbon-Silicon
Similarities and
Contrasts
In view of the extensive chemistry of alkenes it was only natural for organic and
inorganic chemists to search for analogous Si-Si doubly bonded structures. For a
long time such attempts proved to be fruitless. The first stable c-s;s and Si=Si9
compounds were synthesized about a decade ago. One synthesis involves the rearof cycloujsilane:
II is pos.sible to add reagants aCI'OSS the Si= Si double bond in some ways analogous to
the C=C bond in alkenes:
1
rdaliono<hip, like ony othc:r rulc41humb. c:an be seen rram severo! vicwpoin1s: in
..,...,.. of unifYinl known facn (when it wortsJ. as a pn:dic:IOI' or unknown propcnic:s (hoping j(
worbJ, 01' in terms of lhc f4nilicance of iu CICICP.;.,OS (wflcn il does not WO<I<J. Sec. (or example.
TM
Fcinstcin, H. I. J. Qwm. Edur. 1914, 61, 121. Hurus:>, T. P. J. Ch<m. U.c. 1987. 64, 686-681.
Broot, A. G.: Abdcsal<cn. F.: Guldunst, B.:
G.: Kallury. R. K. J. Owm. Soc. Or<m.
Commun. 1981 , 191-192.
9
Wcst. R.; F'onk. M. J.; Mid\1, J. Snmu 1981, 114. 1}43-1:144. M:ls:ulwne. S.; Hanzawa. Y.;
Mutalalmi, S.; Bally. T.; Blounl, J. F. J. Am. Ch<m. Sue. 198%, IIH,
Wcsl, R. Ang<W.
Olf!m. Int. Ed. Enr/. 1987. 26. 1201.
862
18 Periodicity
(18.10)
(18.11)
(18.12)
Compounds that are formally analogous to carbon compounds are foural hl have
monttmcr. but
quit.: diff.:rent structures. Thus carbon dioxide is u
<lim<ide is an infinite single-bondecf polymer. In a similar manner. ll<'m<liols "rc
unstable relative to ketones:
(18.13)
and the analogous silicon compounds are also unsbble. but the "dimethylsilicooe"1
that forms is a linear polymer.
(JIU.Sl
lu The 1cnn "silicone" was coined by 31'01l01Jy 10 kc:Jonc under 1hc mislah'll tx:licf Ihal monomeric
R:Si - 0 compounds could be isolaJcd. Sc:c Chapter 16.
The Use of p Orbitals in p; Banding
863
The contrast between the strengths of 2p.,-2p., bonds and their higher-n congeners is responsible for much of the stability of groups important to organic
chemistry: alkenes, aldehydes, ketones, and nitrites. It also permits doubly bonded
molecules such as carbonic and nitric acids, rather than their onho analogues. A
source of the greater stability of w bonds between the smaller atoms could be better
overlap of the 2p orbitals. The overlap integml f.PAI/Is (see Chapter Sl is o nly poorly
depicted by a drowing such as Fig. 18.1. The overlap is strongly affected by the
magnitude of the wave function in the overlap region and, especially for n bonds. is
increased by small. " llense" orbitals. The first time a given type of orbir.tl
3d. 'If)
appears. it is nodetess and anomalously small. T he small size results from the absence
of inner shells having the same value of I against which this set of orbitals must be
onhogonal.11 The '1p orbitals thus are as small as the 2.! orbital. in contrast to the Jp
orbitals which ure larger and more dilfuse than the 3s
For the heavier congeners in Group IVA (14), the differences are even more
is generally tetravalent e:'tcept as transient carbcne or
striking. Thus. although
methylene
it is possible to pl'epare d ivalent germanium. rin. and lead
compounds. For example. if bulky substituents (R =
are present. the
compounds R.Ge. R,Sn. and R,Pb exist as diamagnetic monomers in solution. although there is a tendency for the-m to dimerize in the solid. The moiC\:ular structure of
the tin dimer has been lletermined and found to be in the trans conformation:
In addition to being bent. in

to cthyl.:ne. th Gc-Ge and Sn-Sn honds are
nul '" short
expected for tnre double bonds.tl Calculations indicate thai p,-p"
bon<ling is less
and other intct-:Jctions may become
imponant.
Cat.:ulatcd bond Mders arc Gc-Ge = 1.61 and Sn - Sn = I ..If!.
ffiffi
II
Pyykk' P. Cltrm. u .. -. l?l!tl...
I!
W:>lsh. R.
ArT.
Fig. 18.1
or
!h.:
pns.<ihly roun:r overlap nf
the p orbitals in Si-Si a.<
compare-d with C-C.
Chrm . Ros. 191!1. 14. 1-ll>. W<.'ll, R. An,:cw. C/tmr. llll. EJ. limtl. 1987. 16.
l:!lll-12tl.
"O..virhon. P. J.: Harris. D. H.: Lnrpcrt. M. F. J. Clorm. S<1c. Dulfon
Cowley. A. H.: Norman. N . C . Pmg. /llt><J:. Clr<m. t91l6. 14, t-63.
1976. 2263-.!.!74.
t Lcndvuy. G. Chrm. Plrys. Lm. 1991. /Ill. IIS-94. See oll;O duta on hond energies M
Cn:v. R. S. AJ1. Ort/ufWiflrt. Chrm. 199t, JJ. I1S-t70.
II6S ond
864
18 Periad icily
Nitrogen-
Analogies and
Contrasts
The slable form of nitrogen at room tempernturc: is N! which has an extraordinarily

strong (946 kJ mol- 1) triple bond. In contrast, white phosphorus consists of P4
molecules (see Chapter 16), and the thermodynamically stable form is black phosphorus, a polymer. At temperatures above 800 c dissociation to P2 molecules does
take place. but these are considerably less stable than N 2 with a bond energy of 488 kJ
mol- 1 In this case, too, in the heavier element several single bonds are more: effective
than the multiple bond .
The phosphorus analogue or hydrogen cyanide can be prepared:
CH4
+ PH 3
.......,
HC= P
+ 3H2
(18.15)
In conlrasl to stable hydrogen cyanide, HCP is a highly pyrophoric 8J1S which polymerizes above - 130 c. In this decade the number of molecules containing C:=P
bonds has increased to over a dozen." One mechod of obtaining them is by
dehydrohaJogenation :
CH1P01
(18.16)
HC=:P
(18.17)
Kinetically slable phosplulalkynes can be synthesized if a sufficiently bulky

substituent (Rl is presenc 16
P 4 + 12Na/K + 120SiMe3
4P(SiMe 3h + 12(Na/K)CI
(18.18)
(18.19)
One of the first challenges facina chemists aucmpting to prepare phosphorus analogues of nitrogen compounds was
First the phosphorus analogue of
pyridine wos synthesized. and now all of the group VA (IS) analogues of pyridine
been prc:paret.l.
0 0 0 0
As
Sb
However, these compounds must be considered the exception rnther-lhun the rule as
far as the heavier- clements arc: concerned.
"Rcsilz. M.; Binc.,., P. I.IIJ(ntf. Clrmt. fnl . Ed. &J/1. 1988. 27, 1484-ISOS. R<gilz. M. Cit-. Rt.
1990, !10, t91. Maah. M. H.: Nixon. J. F. In Tht Cllttrislry of
Compmuuls;
Hnrtlcy. F. R. Ed.; Job. Wiley. New Yorlc, 1990:
9
... Note !hal since a
lot any other triply boMc<t crous>l wid be
end "eposed."
the prOICCiioa Dlforcbl by II bulky ai'OUiliJ is leu than in tbc
d doubly bonded
SpCCies.
li,.....,.
The Use al p Orbitals in Pi Bonding
865
The isolation of compounds containing simple C=P double bonds parallels the
triple-bond work. The first stable acyclic phosphaalkene was synthesized over fifteen
years ago. t7 Again. base-induced dehydrohalogenation and stabili:wtion by bulky
groups is important:
R'
R"
H -C- P/
"
R'/
"a
R'
"
/
R"'
/
C= P
(18.20)
R'
The steric hindrance is critical: If R

phenyl or 2-methylphenyl. the bulkiness is
insufficient to stabilize the molecules. but the 2.6-tlimethylphenyl and 2.4.6-trimethylphenyl derivatives are stable.
Summary on the
OccurTence of
p.,.-p.,. Banding in
Heavier Nonmetals
For many years the occurrence of double and triple bonds such as discussed above for
silicon and phosphorus was equally rare among other nonmetals. leading to the
conclusion that only C=C. C=N. C ;;;;;;O. Ni<:N. etc. were stable multiple bonds.
This. of course. was taken as challenge and much synthetic work was directed at the
problem. None o( the multiple bonds between heavier nonmetals is as strong as those
between the 2p elements. Some typical estimates of the strength of the -rr bond (cf. to
H2C=CH2 as a ' 'standard'' from organic chemistry) are (values in kJ mol- 1) :
C=C
C=Si
C=Ge
C=Sn
272
159
130
Si=Si
Si=Ge
105
105
Ge=Ge
105
79
It now appears that any X=Y double bond can be prepared. given an energetic
enough research allack: Hundreds of these compounds have now been synthesized.
The general method has been to involve bulky substituents. In this way the multiple
bond chemistry of the heavier nonmetals has resembled attempts lo make lowcoordination-number complexes <Chapter 12).
The number of triple bonds of the heavier nonmetals that arc known is considerllbly smnllcr-perhaps a dozen. It has already lx:cn noted abov.: that protecting a
triple bond sterically is considerably more difficult than for the c:tse of :1 corresponding
bond is that. in contrast to the
double bond . One very imerestintt aspect of the
C=C in acetylenes. the triple bond does not ensure linearity at the carbon atom (Fig.
18.2). The reasons are not completely clear but may be related to the nonplanarity o(
R,Ge=GeR. and R.Sn=SnR, (see page 863).
- The
i.solation
all of these compounds is more a tribute to the
persistence with which they were pursued than to any inherent stability o( the bonds
themselves. To invert George leigh MaUory's remark about MI . Everest.the extraordinary efforts expended on this class of compounds stemmed from the fact that they
were not there. These efforts and their correspOnding successes have caused one
observer to comment: "Finding exceptions to the double-bond rule has become a
"Bc:ckcr. 0. Z. AntNg. CMm. lll76. 41J. 247. Cowley, A. H.: Jones. R. A.; U.sch. J. G.: Norman.
N. C.; St'Wilrt, C. A.; Sawn. A. L.; Atwood. J . L.; Huna..-. W. E.; Zllana. H.M. 1. Am. Clwm.
Soc. 1984. 106. 7015-7020.
866
18 Periodicity
fig. 18.2 Mok.-cular

structures of (a)
CF, CeSF, and (b)
l-
SF6 C;gSF1 Crystal

structures are above and
II"S structures below. NO(c
strong bending in the gas
phase. (From Scpp:ll. K.
Angrw. Chrm. Int. EJ.
Engl. t99t, JO. 361- )74.
Reproduced with
pennission.j
to)
spon in maingroup chemistry."t8 but Seppelt. one of the successful synthesizers.

a lso notes: "In spite of all of the remarkable success with the synthesis of such
compounds. the fact remains that these double [and triple) bonds still form. in the final
analysis. more unfavorable bonding systems than those of ele ments of the second
period ."tY
The Use (or Not)

of d Orbitals
by Nonmetals
Theoretical
Arguments against d
Orbital Participation
in Nonmetals
Sevemt workers have objected to the inclusion of d orbitals in bonding in nonmetals .

The principa l objection is to the !urge promotion energy required to effect
(18.21)
where m = 0 (P), I (S}, or 2 (CI), to achieve a maximum multiplicity and availability of
electrons for bonding. A second factor which does not favor the utilization of d
ortlitals the poor overlap that they make with the orbitals of neighboring atoms. The
JJ orbitals of the free sulfur atoms. for example, are shielded completely by the lowerlying electrons and hence do not feel the nuclear charge as much as the Js and Jp
electrons. As a result they are extremely diffuse. having radial distribution maxima at
a dislllnce which is approximately twice a typical bond distance (fig. 18.3). This
in extremely poor overlap and weak bonding. :!a
Two :llcmatives have been suggested to account for the higher oxidation states of
the n.tnanctals: both reduce the imponance of high-energy d orbit:!.. Pauling
suggested that resonance of the following type could take place:
Cl Cl
cr Cl
1/
/
+---+ CI-P
+---+ Fourmorcfonn.ws:
Ekmcnt having" princ.ip:ll qoonlum number grelllcr ahan two are not likely 10 form p.-p. bonds.
IY
Scppelt, K. Angrw. Cllrm. Int. Ed. Enfll. 1991. JO. 361-)64. For recent review,; or some o(
multiply bonded systems, see Niec.k.c, E.: Gudnt. D. An)lrll'. Clwm. lnr. EJ . EnKI. 1991. JO,
S. lh/d. t991 . JO, 902-930: UUIT:lll. J.:
217-237: Tsumuruya. T.: Baachetler. S. A.:
&.:udie. J. ; Sulst. J. Cbrm. 1/rv. t990, 90, 2KJ: lllKI rercr....,.s to cnrli<!r wort< tht:r<'in. Sec also
Footnolc IS.
""These same eencr-aJ atJIIUllCnts apply loa)! of the heavier nonmetals. The dand/orbitals are heavily
!Ohiclde<J by
___ _
The UM (or Not) of J Orbitol by Nonmetols
0.15
867
S-F
D '''
tlp111
.Jistribution
in t/ 1 confiaurotions IAl in the o tc:nn ol P
ol S u'p,d 1) . Line n:presents" typical S- F bond length.
K. A. R. Clwm.
1969, 69. IS7. Reproduced with permission. )
Fig. 18.3 The )d

ts'r'd 1l; tBl in the o
(Moc.lilicd from
d char:>Cter or the total hybrid is small.

Only structure I involves d orbitals . ami
Each P-CI bond has 20"1. ionic character and 1!0'/. covalenl character from resonar>Ce
such as 11 . Paulins has termed the
bonds formed (over 3Ild above
lhe rour in a ooble gas octet or " ursononil:" s tructure) us " lransarsononic" bonds and
pointed wt that they tend to be weke r than " normal" or " argononic" bonds :IIlii
form only with the most elcctroneg:uivc ligmltls. Thus the
bond enefl:Y in PCI)
326 kJ moC 1 but in
it is only
kJ mol- 1 The same effect is round in PF, :lt1d
bm in
case the tliff.:reoc-e in bond .:ncrsy is
kJ mol - 1 c o rresponding
to the stabilization o r the slru.:ture by increased impor13r>Ce of the ionic s tructur.es in
the fluorides. T he stabilization o f thes.:
by tlitrerences in elcctronegativity is
exemplified by lhe tentlcncy 10 form lhe higher lrollc>&en fluorides. The enthalpies of
ftuorination of the halogen monol1uoritlcs a rc:
Clf!gl + :!f :(gl -
CU:, Igl
!J./1 - 152.7 kJ mol-
(18.23)
BrF(g) +
BrF ,tgl
.lll ... - l7t.. l kJ mot-
(18.24)
kJ mut-
(1!1.251
lflgl + :!F:Il:l -
.l/1
The
.l!cru"tiv.: i'
thcc -.:cmcr. fttur-dcctron hunt.! t.levetop.:.J by
nl<llccula r
for Ihe nublc
lluuri..tcs
Ch.,ptcr I ii. Sin'c this
predicts that e:u:h bontling rairor cl.:ctmns
" bontl" l is sp rc.utl o ver three nuclei.
the oon<l between t wo ur the nndci
than that nr" normal two--center. twockcmm bond . Funhcrmoo-c.
the no nbuntlint! puir of electrons is loc .. lizetl on the
Ouorin.: :ttoms. there is a scrar:t ion of charge t" ionic
In both respects.
then. this imcrprctation UllfeCs with Pauling's approach and with the experimental
r..cts.
In the c:ISc of nitr<lgcn.
work intlica h!s that pentac:oordinatc21 and
:1 Chn-.Jc. K. 0 . WibQn. W. W.. S.:htOOolp-n, G . J. : Chirobl . R. V.: Obh, G.
Cll<'m. 1!1811.
17. 7ll'l-'NO. In the f"''t''CN ronlc>J. " f"'nl3 !ur "'" '"''
nitros;cn tc-.wbcln)'' meadS a
nitr<JIICII fcarhlnl u1om with 6vc t>ili OhJnV< hullllcd lo i1 wh h more or""-' locnlizcd sii:Jn:o. bun<ls.
such ;,sin the hypulhc:licod NF,. On the tither hllnd. in the: cntbonlnc. C,8 1,.H 1,. nd :wrbor.lnc.
NS,.H,, . co;ccunopoontb!SChopt..-11\t. lhc l."Ar1>un nd nilrUCCftaiOm.< arc rormallyill.....,._, IO
ax .. ncorcsa nciGf>bor atomli. ;as arc ohc owcla:tronic buroo 3kln\S '" the
borancs.
Ukcwi>c. nu1c " hc\lalcnl CN"ban"
clu>lcrC0<\'4)IlUndltCbaptcr t51 and in the
compounds !sec P'IC HIISt.
in '""'""'
868
18 Periodidty
hexacoordinate nitrogen do not occur. On the other hund, a theoretical case has been
mude for the pOSsibility of pentacoordinate nitrogen in a molecule such as NF,.n
Experimental
Evidence for d.,- p.,
Bonding; the
Phosphorus-()xygen
Band in Phosphoryl
Compounds
In the case of d,-p., bonding we again lind the old problem of detecting the existence
of a bond . We can infer the presence of a u bond when we lind two atoms at distances
considerably shorter than the sum of their van der Waals radii-. The detection of a 1T
bond depends on more subtle criteria: shortening or strengthening of a borJd, stabilization of a charge distribution, etc . experimental data which may be equivocal.
One example of the apparent existence of 1T bonding is in phosphine oxides. Most
tertiary phosphines are unstable relative to oxidation to the phosphine oxide :
(18.26)
This reaction takes place so readily that aliphatic phosphines must be protected from
atmospheric oxygen. The triarylphosphines are more stable in this regard but still can
be oxidized readily:
)
KlloW)4
(18.27)
In contrast. aliphatic amines do not have to be protected from the atmosphere

although they can be oxidized:
R1 N + HOOH- (R1 NOH]+oH-
-H.O
R1 NO
(18.28)
However, the amine oxides decompose upon hea ting:

EtlNO
Et1 NOH + CH1 =CH1
(18.29)
a reaction completdy unknown for the phosphine oxides, which are lhermally stable.
In fact, the tertiary phosphine oxides form the most stable class of organophosphorus
compounds. Those oxides with no J3 hydrogen atom are particularly stable : Trimethylphosphine oxide and triphenylphosphine oxide do not decompose below
700 c.n They are not reduced even by heating with metaUic sodium. The tendency of
phosphorus to form P-.0 or P=-0 linkagesl is one of the driving forces of phosphorus chemistry and may be used 10 rationalize and predict reactions and structures.
Fur example. the lower phosphorus acids exist in !he four-coordinate structures even
though they are prepared by the hydrolysis of three-coordinate halides:
(18.30)
(18.31)
:2
Zl
Ewig. C. S .; Van Wazer, J. R. J. Am. Clwm. Soc. tM , ttl. 41n4t78.

Pltorp/IDflls. 4th cd.: ElscvCt: Atratenlam, t990; P no.
Cbridc. o . E.
c.
,.. Who:thcr the P-0 bond ;. essentially u slnclc. " dulive bond, P....O, hu at least some J.,-p
clooble-bond dlaracteo- is. or coun<:,lhc IIIJIInltftt
unci to ponnly Ihe rollowingstructures wilh
eilher P-0 or J>-0 lmds to anticipate the quesalon ...,inlenlionolly: See lhc I'C$Ofi1I1Ce
In
Eq. t8.36.
ronns
The Use (or NotJ of J Orbitals by Non-tols
X
.I':P'\. f/X
P
X
/ OH
...,..P- P-OH
[ HO/
HO
xl
0II 0II
_____. H-P-P-H
HO
869
(18.32)
OH
The tendency to form P=O bonds is responsible for the Arbusov reaction. The
typical reaction is the rearrangement of a trialkyl phosphite to a phosphonate:
0
(R0)3 P
II
(R0)2PR
(18.33)
If the catalytic amounts of RX in Eq. 18.33 are replaced by equimolar amounts of R' X.
the role of the alkyl halide in the formation of an alkoxy phosphonium salt is revealed:
R'X [RO-t-} x- -
RO - P-R' + RX
(18.34)
Oxidation of trialkyl phosphites by halogens illustrates the same principle:
(RO),P + 0
2 --.
[(RO),PCJ)a- -
(RO)zP(O)CJ
+ RCI
(18.35)
A final difference between nmine oxides and phosphine oxides lies in the polarity
of the molecules. The dipole moment of trime.t hylamine oxide is 16.7 x 10-30 C m
(5.02 0) compared with 14.6 x 10- 30 C m (4.37 0) for triethylphosphim: oxide. A
consequence of this polarity is the tendency of the amine oxides to form hydrates,
R3NQ-H20. and their greater basicity relat.i ve to the phosphine oxides.
The difference between the behavior of the amine oxides and phosphine oxides
can be rationalized in terms of the possibility of buck bonding in the Iauer. Whereas
umine oxides arc restricted to a single structure containing a dative N-0 bond.
R3 N-O. the phosphine oxitles can have contributioM from d"-p" bantling between
the phosphorus anti oxygen atoms:
R P--+o- ,___. R3 P= O
3
(I)
(18.36)
(0)
The double bond character introduced by the Jailer strengthens the bond and accooots
for the extr.wrdinary stability of the phosphorus oxygen linkage. Note that this ex tra
stability cannot be attributed to ionic resonance energy (a priori a reasonable suggestion since the difference in elcctronegativity is greater in P-0 than N-Q)
because the dipole moment of the nitrosen compound is greater than that of the
phosphorus compound, a result completely unexpected on the basis of elec
tronegativities, unless consider.llion Is taken of canonicnl form 18.36(11), which would
be expected to lead to a reduced moment.
A comparison of the bond energies also supports the above inlerpn:tation. The
dissociation energies of P=O bonds in a variety of compounds lie in the range of
500-600 kJ mol- 1 compared with values for
of about 200-300 kJ mot-. The
value for the IaUer is typical of what we miaht expect for a sin&Je bond, but 600 kJ
870
18 Pe nodicity
mot- is scronger Ihan any known single bond (see Chapter 8). A closer examination of
the strengths of various P-=0 bonds in tenns of infrared stretching frequencies shows
some interesting trends. For a series of similar molecules, r.uch as the phosphine
oxides. the stretching frequency provides an indicacion of the strength of the bond
(Table 18.2)2.!1 The highest stretching frequency among the phosphoryl compounds is
that of F 3PO, and the lowest of the halides is that of Br>PO (the iodo compound is
unknown). When the stretching frequencies are plotted as a function of the sum or the
electronegativities of the substituents, u struight line is obtained:
VPO
= 9JQ
+ 401:x
(18.37)
where xis the Pauling electronegativity of a substituent atom-or group on phosphorus.

The correlation between the elec.t ronegativity of substi tuent groups and the
strength of the P=O bond provides support for a tT-bonding model but not for the
alternative dative u-only model. A u bond might be expected to be destabilized as
electron density is removed from the phosphorus, requiring it to withdraw electrons
from the P-+0 bond. weakening it. ln contrast. if the oxygen can back bond to the
phosphorus through a d-p 1r bond. the induced charge on the phosphorus can be
diminished and the P=O bond strengthened.
The bond lengths in phosphoryl compounds are in accord with the concept of
double-bond character. In the simplest case, that of P4 0 10, there are two P-0 bond
kngths. There are twelve relatively Ions ones ( ISS pm) within the cage framework
propel' and four shorter ones ( 141 pm) between the phosphorus atoms and the oxygen
atoms external to the cage. It is interesting to note that the ratio of these two bond
k'flgths (0.89) is about the same as
to
ur
to
lsoelectronic with the phosphine oxides are the phosphorus ylids , R3 PCH!. As for
the oxides, two resonance forms
c- c c-c c-o c-o.
(18.38)
til
(II )
Tobie 1;..:8.;..:2_ __
lnftorud stretching
frequencies ol some
phosphoryl compounds"
FPO
)
F.CIPO
ci,ro
1404
11.70
1358
l0.7S
8.85
8.52
8.t9
8r1 p0
1295
1285
1275
1261
1190
7.86
(7.2)
Me1PO
1176
(6.0)
CI. Bt-PO
OBr,PO
Ph3 PO
'"''R'JI.
" Noto tbul the Jl,.><iution

R,PO- R,P + 0 not a tcMitivc mcMun: ol'the P-O bond
l1cc.uk the r<li'Ciinina three bonds rroy be
vr wukened in the diMoc:i:uion
proceu. The IR olrckhitc frequency
ol'the lOree consunt.lt. and the reduced mass.,._
olthe vibrolingsroups. lrthe mokculc iu..umat
.
to be
oxwcnatom vibr:>lin11.onu fixru"
WQ;cr mlS$Ofthc R3P group. the rccb:al m:w b con.aunt. lnd
frcqiJC11CywiP rellca
ch:lrces in the fllt'Ce wn5t:UU. For >imolill ndcaJics the force c:am.ont wid be rdated
to the total bond COCI'lY.
u" runaioo
!ish
The Use (Of Not) of J Orbitals by Nonmetals
871
contribule to the stability of the phosphorus ylids but OOl the corresponding ammonium ylids, R3N+-C-Hz. This difference is reflected in the reactivity. The
ammonium ylids are generally quite basic arid quite reactive; the phosphorus ylids are
much Jess so, many not being sufficiently basic to abstract a proton from water and . in
fact, not dissolving in water unless strong acids are present.
A Comparison
of Pi Bonding
in Phosphine
Complexes and
Oxides
The controversy over the nature of the P=O bond is reminiscent of that over the
nature of phosphorus-metal bonds in coordination compounds. In both. interpretations have long ranged from a u-only to a highly synergistic U-'IT model. As we have
seen in Chapters II and 15. u orbitals have also been invoked in mQf"e recent
phosphorus ?T bonding arsuments. inasmuch as d-u hybrids may be involved.!" So
the question turns out not to be simply u vs. ?T but the relative contributions of d and
u orbitals to the latter. As with so many questions in inorganic chemistry. the answe.is neither black nor white. but gray. If the symmetries and energies of orbitals are
compatible. bonding will occur. The appropriate question is one of relative
importance.
Evidence from
Bond Angles
The trimethylamine
has a pyramidal structure much like that of ammonia
with a CH 3-N-CH3 bond angle of 107.8" 1. In contr.lst. the trisilylamine
molecule is planar. Although steric effects of the larger silyl groups might be expected
to open up the btnd angles. it seems hardly possible that they could force the lone pair
orbital an<l make the molecule perfectly planar te,en
out of a founh
Ph,N has bond angles of 116"!. It sc.:ms mOf"e likely that the lone pair a<lt>pts a pure p
orbital on the nitrogen atom t>ccause orbitals on the three silicon atoms C3n overlap
with it an<l dt:lQClllizc the lone pair over the entire system (F"Jg. 111.4).
/s.u.
' s;u,
H,St=N
Fig. 18.4 Dck>caliLation or the

p.., orhiaal..
Ovcrtp of''"'
rcir in tri,ilyt amine. hll Resonance stmcturcs. Chi
::.. Orpen, A. G. : ConncUy. N. G. J. Clum. s..c . Clll'm. C.tmmun. t915. IJt0-131 1. P'.Kchioni. G.;
P. S. lniW}l.
1992. Jl. 4391-098.
87l
18 Periodicity
Rather similar results are obtained by comparing the bond angles in the silyl and
methyl ethers (Fig. 18.S) and isothiocyanates (Fig. 18.6). In dimethyl ether the oxygen
is hybridized approximately spl with two lone pairs on the oxygen atom as compared
to an approximate sp2 hybrid in disiloxane with.,. bonding. In the same way the methyl
isothiocyanate molecule. CH1 N=C=S. has a lone pair localized on the nitrogen
atom, hence is bent (N - sp2), but the delocalization of this lone pair into a ?T orbital
on the silicon atom of H 1SiN=C=S leads to a linear structure for this molecule.
The hypothesized delocalization of lone pair electrons in the above silicon compounds is supported by the lowered basicity of the silyl compounds as compared to the
cOITesponding carbon compounds. This reduced basicity is contrary to that expected
on the basis of electronegativity effects operating through the u system since silicon is
less electronegative than carbon. It is consistent with an "internal Lewis acid-base"
interaction between the nitrogen and oxygen lone pairs and empty acceptor d orbitals
on the silicon. Experimentally this reduced basicity is shown by the absence of
disiloxane adducts with BF3 and BCI:J:
(CHJhO + BF1
{CHJ20-+BF3
(18.39)
+ BF3
No adduct
(18.40)
(SiH 3h0
and by the absence of trisilylammonium salts. Instead of onium salt formation trisitytamine is cleaved by hydrogen chloride:
(111.41)
Pi Bonding in the
Heavier Congeners
In view of the uncertainty with which ?T bonding is known in the very weU studied
phosphorus and sulfur systems. it is not surprising that little can be said concerning
the possibility of similar effects in arsenic. antimony. selenium. tellurium. etc. In
general it is thought that the problems faced in phosphorus and sulfur chemistry
concerning promotion energies and diffuse character may be even larger in the heavier
congeners. In the latter reprd it is interesting to note the apparent effectiveness of ?T
bonding in metal complexes. To the extent that softness in a ligand can be equated
with the ability to accept electrons from soft metal ions in d,.-d,. "back bonds,"
information can be obtained from the tendency to complex with (b) metal ions (see
Chapter 9): P > As > Sb. This order would indicate that the smaller phosphorus atom
can more effectively ?T bond with the metal atom.
Fig. 18.5 Compari.s on of

the
structures of
dimethyl ether and
disitoxane.
C"H,
o-c=s
F;g. 18.6 Comparison of

- the molecular llructures d
methyl isolhiocyanate and

lily! isotlliocyanatc:.
The Use lor Na t) of J Orbital by Nonmetals
873
Theoretical
Arguments in favor
of d Orbital
Participation
In contrast to the arguments prese.nted aaainst participation by d orbitals in the

bonding of nonmetals. several wori<ers have pointed ou t that the large promotion
energies and diffuse character described above are prop;mies of an isoluud sulfur or
phosphorus atom. What we need to know are the
of a sulfur atom in a
molecule, such as
or PF,. This is an exceedingly d ifficult problem and cannot be
dealt with in detail here. However. we have seen how it is possible to calculate such
properties as electronegativity on isolated atoms as charge is added or withdrawn
such properties in a molecular
(see Chapter S) and how this might
environment.
II is apparent from the preceding discussions that participation of d orbitals, if it
occurs at all. is found only in the nonmetals when in high oxidation states with
electronegative substituents. The partial charge induced on the central P or S atom
will be large merely from che eleclronegalivity of the fluorine (as in PF5 SF;,) or
oxygen (as in OPXl
irrespective ohny bonding model rsuch as Pauling's or
the three-center bond) invoked.
We have seen in Chapter 2 that increasing effective nucleat charge makes the
energy levels of an a com approach more closely the degenerate levds of the hydrogen
atom. We might expect. in general. thaJ increasing the effective nuclear charge on che
central atom as a result of inductive effects would result in the lowering of the d
orbitals more than I he corresponding s and p orbitals since the former are initially
shielded more and hence will be rnorr sensitive to changes in electron density. Tile
promotion energy would thus be lowered. A second effect of large partial charges on
the central atom will be a shrinking of the large. diffuse d orbitals into smaller. more
compact orbitals that will be more effective in overlapping neighboring atomic orbitals. For example. sample calculations indicate that in SF6 the d orbitals h:IVe been
contracted to an extent thai the radius of maximum probability is only 130 pm
compared with the large values of 300-400 pm in the free sulfur atom (Fig. 18.3).
Experimental
Evidence for d
Orbital Contraction
and Participation
One of the most remari<able molecules is thiazyl trifluoride, NSFl (fig. 18.7). This
compound is very stable. It does nol react wilh ammonia at room temper.llure. with
below
hydrogen chloride even when heated . or with metallic sodium at
400C. The S- N bond. 141.6 pm. is the shortest known bet ween these two elements.
The FSF bond angles of 94 are compatible with 11pproxim:11e spl bonding n nd the
the
presence of an .rp' hybrkl "bond und t wo p..J ,. bonds between the sulfur
nitrogen. The conlrat lion of the d orbitnls by the inductive effect of t.he lluorine moms
presumably permits effa:tivc overlap and ,-.bond formation. The uhemalive explanu
lion would require a double dative bond from the sulfur atom, extremely unlikely in
view of the positive character of the sulfur atom.
The bond length is consistent with a triple bond. Bond lengths of 174 pm for single
S-N bonds (in NH2SOlH ) and IS4 pm for double S=N bonds (in N4S4 FJ are
consistent with a bond order of 2.7 in lhiazyl trifluoride. This value is also in
agreement with an estimale based upon the force constant. The relative bond lengths
of S-N. S=N. and S;;;;;;N bonds are thus 1.00:0.88:0.81 compared with similar
s hortenings of 1.00:0.117:0.78 (or corre$pondil18 C-N, C=N, and C.,.N bonds.
Fig. 18.7
M olecular
slnlcture ollhiazyl
trifluoride, NSF,.
87 4
18 Periadicity
Two other molecules

the influence of fluorine substitution on d orbital
participation are S4 N4 H4 and N4 S4 F4 (see Chapter 16).
tetraimide is
isoelectronic with the S,. molecule and so the structure
S- N- S
H-N
N- H
S-N-S
H
and corresponding crown conformation appear quite reasonable. The fluoride. however. has an isomeric structure with substitution on the sulfur atoms:
F - S= N - S- F
II
I
N
II
N
I
F - S-N = S- F
Double bonding in this molecule clearly shown by the alternation in S-N bond
lengths in the ring (see Fig. 16.30bl. Now bOih the above electronic structure for
S 4 N4 F4 and that for S 4 N4 H 4 are reasonable but
the question: Why doesn't
tetrasulfur tetraimide isomerize from the N-substituted form to the
form
isoelectronic with the fluoride:
H-S=N-S-H
II
'I
H-S- N=S- H
retaining the same number of u bonds and gaining four w bonds'! Apparently the
reasnn the isomerism does not take place is that although ,. bonding is reasihlc in the
presence of the eleccronegative Huorine utoms. it is so weak with eleccropositive
hydrogen substituents Ihal it camot compensate for the weakening of the "bonding as
the hydrogen atom shifls from the more electronegalive nitrogen alom to lhe less
electronegative sulfur atom.
Presumably subslilulion by halogens in the phosphazene series results in contracted d orbitals and more efficient w bonding in the ring (see Chapter 16).
metrical substitulion may allow the normally planar ring to bend. A good example of
this is found in
Ph
Ph
'-/
p
t/
F.._ n
F
p
p
/ ' #''
N
lteacthrity and J Orbital Participation
875
The three nitrogen atoms and the ftuoro-substiluted phosphorus atoms are coplanar
(within 2.S pml. but the phenyl-substituted phosphorus atom lies ZO.S pm above this
plane. The explanation offered is that the more electropositive phenyl groups cause an
expansion of the phosphorus d orbitals. less efficient overlap with the p orbitals of the
nitrogen atom, and a weakening of the., system atthlll point. This allows17the ring to
deform and the
moiety to bend out of the plane.
Further examples of the jeopardy involved in casually dismissing d orbitals
participation are the findings of Haddon and coworkers2 that d-orbital participation is
especially important in
which is nonplanar. and also that it
for about
one-half of the delocalization eneray in the one-dimensional conductor (SN)..- In the
Iauer case. the low electroneglllivity of the d orbitals (see Chapter S) increases the
ionicity of the S-N bond and stabilizes the structure.
Finally. it will be recalled that the existence of strong P-O bonds in OPF) (see
page 870) is consistent with enhanced b01ck
of electron density from the
oxygen atom to the phO!Iphorus atom bearing a positive partial charge from the four u
bonds to electroneplive atoms. In tight of the above discussion the contrxtion of
phosphorus and sulfur d
when bearing a positive charge. bener oerlap may
be :ldded to the previous discussion as a second factor stabili1:.ing this molecule.
The question of d orbitnl participation in nonmetals is st.ill an open controversy. In
the case of u-bonded species such as SF6 the question is not of too much imponance
since all of the models pt"edict an octahedral molecule with very polar bonJs. P:lf.
ticipation in ,. bonding is of consi<lerably more interest. however. Inorganic chemists
of a more theoretical bent tend to be somewhat
feeling that the
regarding promotion energies and poor overl;,p have not been adequately sol\'ed. On
the other hand. chemists interested in
and characterization tend to favor the
use of d orbitals in describing these compounds. pointin& to the
heuristic value
that has been provided by such Jescriptions in the p<\St and arguing that until rigorous
and complete calculations on these molecules
the ubscnce or significant d orbital
participation it is too soon to abandon a useful model.
or
Reactivity and
----
dOrbital
Participation
---
It hus been pointed outt.h.lthc

of the M:.;ond row 1Lito Fl not only resemble
their heavier congc:n.:rs to a .:ertain <:Menl las far
formaloxiJation stat.:. at least)
hut :11\o 1bc luw.:r ri!lht Jiugnml ct.:mcnt (as f:tr as
sile. uml clcctronegalivity
arc concerned). For ex:mpfc. both silicon un<l
form hy<lridcs tlwt have
some properties in common with ulkuncs.
t hey are much
smble. As a
result of the electronegalivity relationship the P- H bonJ more closely approac:hes
the polarity of the C-H bond than doe the Si - H bond . The
of
phosphorus to carbon has even been extended to the suggestion that a discipline be
built around it in the same manner as organic chemistry is built on carbon.
There ;,. on.: important aspect
the c hemistry of both si licon and phosphorus
which differs markedly rrom that of carbon. Consider the following renctions :
or
CCI4 + H!O - - No reaction

SiC!
+ 4H!O -
+ 4HCI
(IKAZ)
(IK .43)
N01e llwllhis cpbt\;ltion <lo.: not

the prc>ence o/ lhc
ollhl:
cuiU<'s
!he: rin11
it. pc:rhilp5 rc:..
from cryltol I""Ckif1s forces.
311 Hotldon. R. C.; Wassenn;,n, S. R.: Wwl. F.: Willoams. (j, R. J. J. lim. CMM. SO<. t980, 102.
!7
6687--66113.
87 6
18 Periodicity
PCJ5
..;;;!: 2HCI + OPCI,
(18.44)
0P(0Hh
In contrast to the inertness of carbon halides. the halides or silicon and phosphorus are
extremely reactive with water. to the extent that t hey must be protected from atmospheric moisture . A clue to the reactivity of these halides is provided by the somewhat
similar reactivity of acid halides which readily react with water:
o-
II
RCCI + H2 0 _____. R-C-CI
II
---t
6+
R - C-OH HCI
(18.45)
/'-H
The unsaturation of the carbonyl group provides the possibility or the carbon expanding its coordination shell from 3 to 4. thereby lowering the activation energy. Carbon
tetrahalide cannot follow a similar path, but the halides or silicon and phosphorus can
employ JJ orbitals to expand their oelets:
Cl Cl
,,
I/
O- P
Cl O
,,/
Cl Cl 0
+ HzO
->
/ l' o
0 0
- - + OPCI,
+ 2HCI, etc.
(18.46)
This enhanced re-dctivity of compounds of silicon and phosphorus is typic-.sl of all

the heavier nonmetals in contrast to the elements of the second row.
Pe riodic Ano m alies

of the Nonmeta ls
and Post1ra nsition
Metals
or
It is generally assumed that the properties of the various families of the periodic chart
change smoothly from less metallic (or more electronegative) at the top of the family
to more metallic tor less electronegative) at the bollom oft he family. Certainly for the
extremes of the chart-the alkali metals on the left and the halogens und noble gases
on the right-this is true; t he ionization potentials. for example, vary in a rather
monotonous way.
is not true for certain cent ral parts of the chan. however.
Relucta nce of
There is a definite tendency for the nonmetuls or the fourth row-As. Se, aml Br- to
be unstable in their maximum oxidation state. For example. the synthesis of arsenic
Fourth-Row
allhough both PC Is antJ
Nonmetals to Exhibit penlllChloride eluded chemists until comparatively
arc stable . The only stable arsenic pentahalide is AsF5 : As0 5 decomposes at
Maximum Va lence
-so "C. and AsBr5 and As l5 are still unknown.
In Group VIA (16) the same phenomenon is encountered. Selenium trioxide is

thermodynamically unstable relative to sulfur trioxide and tellurium trioxide. The
enthalpies or formation of
SeF6 , and TeF6 are - 1210. - 1117, and -1320 kJ
mol- 1 respectively. This indiC3tes comparable bond energies for S-F and Te-F
bonds (317 and 330 kJ mol- 1, respectively), which are more stable than Se-F bonds
(285 kJ mol- 1 ) .
"Scppdt. K. Z.
CM"m. tm, 4.U, 5.
Pariocroc Anomali.. of the Nonmetals and Posllranoitian Metals
877
The best known exceptions to the general reluctance of bromine to accept a + 7

oxidation state are perbromic acid and the perbromate ion. which were unknown prior
to 1968 (see Chapter 17). Their subsequent synthesis has made their nonexistence
somewhat less crucial as a topic of immediate concern to inorganic chemists, but
bromine certainly continues the trend started by arsenic and selenium. Thus the
perbromate ion is a stronger oxidizing agent than either perchlorate or periodate.
Anomalies of
Groups IliA (13)
and IVA (14)
Before seeking an explanation of the reluctance of As. Se. and Br to exhibit maximum
oxidation states, a related phenomenon will be explored . This involves a tendency for
germanium to resemble carbon more than silicon. Some examples are:
I . Redudion ofIra/ides (X) with line and hydrochloric acid.
bles carbon and tin resembles silicon:
/
HC1
Germanium resem-
(18.47)
's x --oo-+
z. No "'/
' sa- H
(18.48)
)Ge- X
)Ge-H
/
(18.49)
No --;Sn
'
- H
(18.50)
'/ 1-
--;Sn
'
- X
--oo+
z.
2. Hydrolysis of the f<tralaydridcs. Silane

in the presence of catalytic amounts of hydroxide. In contr.ast. methane. germane. and stannane do
not hydrolyze even in the presence of large amounts of hydroxide ion.
3. Reaction of organolithium <ompomtds willt (C6 H,11 MH. Triphenylmethane
and triphenylgermane differ in their reaction with organolithium compounds
from triphenylsilane and triphenylstnnnaoe:
Pll 1CH
+ LiR - - . l.iCPhl + RH
Pll-'SiH
+ LiR--+ Ph)SiR + LiH
Ph.,GeH + l . i R - LiG.:Ph, + RH
Ph1SnH
+ l.iR -
Ph1 SnR
+ LiH
(18.51)
(18.52)
Ph>GeGel'll1 + LiH
(18.53)
(18.54)
4. Alwrnation in entlta/pies a/formation. There is a tendency for the enthalpies

of formation of compounds of the Group IVA ( 14) elements to alternate from
C-Si-Ge-Sn-Pb. Although closely related to the previous phenomena. this
variation is also related to the .. inen pair effect" and will be discussed further
below.
The elements of Group IliA (13) show similar properties. although. in general. the
differences are not so striking as for Group IVA ( 14). It may be noted that the covalent
radius of gallium appears to be slightly smaller than that of aluminum in contrast to
what might have been expected. The first ionization energies of the two elements are
close (578 and 579 kJ mol- 1), and if the sum of the first three ionization
energies is taken. there is an alternation in the series: B 3 6887, AI ,. 5139, Ga 3
5S21,1n = S084. Tl = 5438. kJ mo1 1
878
18 Period icity
The " Ine rt Pair

Effect"
Arnone the heavier posUransition metals there is a definite reluctance to exhibit the
highest possible oxidation state. Thus in Group IVA ( 14), tin has a stable + 2 oxidation
state in addition to + 4, and for leud the + 2 oxidation state is far more important.
Other examples are stable n + (Group Ili A, 13) and Bi1+ (Group VA, 15). These
oxidation states correspond to the loss of the np electrons and the retention of the 11s
electrons as an " inert pair" .JO
II can readily be shown that there is no exceptional stability (in an absolute sense)
of the s electrons in the heavier elements. Table 18.31ists the ionization energies of the
valence sheU s electrons of the elements of Groups IliA (13) and IVA (14). Ahhough
the 6s electrons are stabilized to the extent of - 300 kJ mol- 1 (3 eV) relative to the Ss
electrons, this cannot be the o nly source of the inert pair effect since the 4s electrons
of Ga and Ge have even gre.a ter ionization energies and these elements do not show
the effect-the lower valence Ga(l) and Ge(ll) compounds are obtained only with
d ifficulty.
The pragmatic criterion of the presence or absence of an inert pair effect can be
taken a.s the tendency (or lack thereoO for the following reaction to proceed to the
right:
(18.55)
We might then inquire as to the systematic variation in thermodynamic stability of the
higher and lower halides of these elements. Titere seem to be two seneral effects
operating. The combination of the two effects gives irregular chunses in cov.tlent bond
energies (see Table 18.4). The simplest is the tendency for weaker covalent bond
romuuion by larger atoms (see Olapler 9). The second is the "anomalous' propenies
of those elements that follow the first fillif11 ofa given type of orbital Is. p , d./ . ..) .ll
All of these elements exhibit a lower tendency to form stable compounds than do their
lighter and heavier congeners. Both sodium and magnesium form less stable compounds than would be expected, when compared to lithium ami beryllium. or potassium and calcium.n These elements are those that follow immediately after the first
fillins of a set of p orbitals (NeJ, and the same effects of incomplete shielding llhough
less pronounced to be sure) presumably are opernting here as well as in the
postlanthanide and postscandide elements. This principle hns also been used to
some of the chemical properties of t he superheavy truns:1ctini.Je elements.
Tobie 18.3
loni>atK>n energies ol s
electrons in kJ mal - 1 IVJ
Element
B
AI
Ga
In
Tl
IE2 +IE,
6.087 (6]. /)
4,561 (47.3)
4,942 (.S/.2)
4.526 (46.9)
4,849 (50.3)
Elemant
IE,+ IE.
I0,843 I11 2.4)
Si
Ge
Sn
Pb
7,S87
7.712
6,873
6, 165
(78.6)
(79.9)
(7/ .2)
(6].9)
"'This is also rdatcc! to thoo (a<:t thal "RzSn-SnRl" c:ompcl<lnds may exi51 M R:Sn
in 50luti<Jn
11"'1" 8fill. Closely rctued, bill IIIli identical, is the ract thW an unoxidiud .r electron p:lir ""'Y or
rmy nut be
..:11..:. See diocii$Sions ill 0..'J'Ien 6 and 17.
Jl Huhcey. J. E.: Hlllecy. C. L J . CAm. Jut. t97l. 49, 227.
"EY11t1s, R. S.; Huhy, J. E. J . lrttJI'I. Nltd. Clkm. 1970, JZ. n1.
Periodic Anomalies of the Nonmetals and Pasttransitian M.tals
Tal>le 18.4
Bond -sin of some group IVA (14) halides in 1<.1 mol- l (kca/ mof-1)
EJ.m.nt MF,
MO,
MC(o
Mlr2
Mf
Si
565 (135)
381 (9/)
481 (11.5) 452 (/08) 385 (91.0) 349 (83.4) 326 (77.8)
Ge
481 (1/.5) 414 (98.9) 386 (92.2) 323 (77.2) 329 l78.n
Sn
Pb
394 (94.2) 331 (79./ ) 304 (72.6) 243 ($8.1) 260 162.2)
M
310 (74)
1:76 (66.0)
1:73 (6S.2)
201 (48.0)
Ml,
.....:
879
Mf
--234
264 (6J./) 212
262 (62.S) 205
20.S (49.0) 142
(5.5.9)
(50.6)
(49.0)
(33.9)
FOf" the lighter elemenls these effects can relldily be fOf"mulated in terms of
ordinary shielding effects as discussed in Chapter 2. For heavier eh:menls , however,
the theory of relalivily must be invoked.
Re lativistic EHects
Normally the theoretical basis of chemistry is the nonrelalivistic SchrOdinger equation. To this are added the postulate of elec tron spin and ideas related to it such as the
P..wli exclusion principle. Although the laner arc: thus seemingly ad hoc ""add ons to
make the theory work. mllst of the theoretical chemislry has been done on I his basis.
The corresponding rel:uivistic approach yields the Dirac equation.Jl This gives four
quantum numbers directly. although only the principal quantum number- n is the same
in both treatments. The relativistic treatment results in a number of novel effects, both
descriptive"' and theoreticalH mosl ol which can usually be neglected with liule Joss
of accur.lCY and a great gain in convenience. There are two
to this
generalization however. One is spin-orbit. or jj, coupling (see Chaplcr II and Appe.ndix C). The
is that neslect ol relativistic effects becomes increasingly serious
as the atomic number incrc:1ses. The s land ro a slightly lesser ex tent, p) electrons will
accc:lerate greatly as they approach the nucleus. and their speed relative to the fixed
speed of light
be ignored. II hus been estimated that for mercury (Z = 801 the
speed ol a Is electron is llver half that of light. This results in an approximately 20"/.
in electronic mass and
approximale.l y 20% decrease in orbital size.l61 n the
simplest c:ose we can lillY lh:lt .f und p orbital$ will contracl . and I hat d andforbilals
will expand somewhat. The seem ins puradllx that the d und f o rbituls e.tpund instead
or conlr:.ct is
intlirt elf. Dirccl relativistic effects un J und f ori>ilals are small
bccaus.: these orbitals do not have: electron denMity ncar the nucleus. However. the
''Dink:. P. A.M . Pmc-. R. SH. L11ntlun. Srr. A t92ll. Jl//7. 1110: 1921. All8. lSI .
" Some of the::. socii a.< ohc: bet, lhnt &<li<J mo:tl ha.< its fmiliar color and th:ll mercury mct;d is a
li<juN. f.-.11 ouo>i<Je the SCOpe of this !ext. S Pyykko. P.:
J.-P. Mr. cm. Rrs. 1979. 12,
Othc:n. will hc: <liscu.<scd l>dow.
tOC.C ore: All houGh the:
number I <liU del ermines O<tiaal twc u.p . J,f . .. ). il no
lonscr clctcrmin.: <>rl>ilt
AU <Jibibls of lo:iven vntue d n and I no Junsct hove: the: same
encflics. Orhilnl h.pc
1-ychc: unll,Uturmcmentum quantum numbctj alld the:
quantllrll number m. The: sllnpeo of crtiouls ate not the fmiliDr end Given by the: SchrOdingor
eqwlion, but sc:emios)y "misslwpen" IIO<Ic:less llnUJoaues. Se1: 1\!c:Kelvey, D. R. J. Orm. Educ.
19liJ. 60. I t2-116; rUWdl. R. E. lbiJ. 1963, 4J
" Some
lfl This
'h:'""
. - . re:Mllty _,. from the: in\'<:r>e relaJioNhip between Rollr radius unci mass (a, =
4wfllllfiZr!).
880
18 Periodicity
increased shit!lding of d and f orbitals by relativistically contracted s and p orbitals

tends to cancel the elfect of increased
So the sandpelectrons are moved closer to
the nucleus. their energy is lowered (made more negative). and they are stabilized.
The d and f orbitals are raised in energy (destabilized) and expand . Since the
outermost orbitals are the ns and np rather than the (n - 1)d or (n - 2){. each atom as
a whole contracts.J8
The relativistic effect goes awroximately as r-, and this is the reason for its
importance in the heavier elements. In terms of energy and size, it starts to become
important in the vicinity of Z = 60-70, contributing perhaps an additional 10"/. to the
nonrelativistic lanthanide contracllon (see Cllaptes- 14).l9 As we have seen, this results
cancellation of the expected increase in size with increase in n from
in an almost
zirconium to hafnium.
While the contraction resulting from the pOOr shielding of 4f electrons ceases at
hafnium,lhe relativistic effect continues across the sixth row of the periodic table. It is
largely responsible for the stabilization of the 6$ orbital and the inert s pair effect
shown by the elements Hg-Bi. 11 also stabilizes one-40 of the 6p orbitals of bismuth
aU owing the unusual +I oxidation state in addition to + 3 and + S.t
z.n
"Anomalous"
Ionization Energies
and Electron
Affinities
Many introductory chemistry books give simple rules for remembering the periodic
changes of ionization energies and electron affinities. The rules usually follow some
modification of "Ionization energies and electron affinities increase as one moves to
the right in the periodic chart; they decrease as one moves from the top to bottom."
These generalizations, as well as the shielding rules that account for the atomic
behavior. were discussed in Chapter 2. along with some of the exceptions. Unfortunately for simplicity. the exceptions are somewhat more numerous than is generally
realized . Many of the problems discussed in the preceding sections result from these
"exceptions."
The horizontal behavior of atoms follows the general rule with good regularity as
might be expected from adding a single proton at a time with expected monotonic
changes in properties. We have already seen the exception of the inversion of the
ionization potentials of the VA (15) and VIA (16) groups related to the stability
associnted with half-filled subshells. A similar inversion of electron affinities takes
place. for the same reason. between groups IV A (14) and VA (15).
The ven ical exceptions to the generalizations are much more widespread: If we
count every time that a heavier element has a higher ionization potential or higher
electron afllnity than its next lighter congener. we find thai about one-third of the
show "electron affinity anomalies"4 2 and a sumewhat higher fraction of the
elements shuw "ionization energy anomalies." With
a high frnctiun of excep-
J>
K. S . A.-c. C/Nm.
t979. 12. 271-276. See also Foo1no1c 34.
,. NOIC from Fipe 2.4 how lhc maximum eleclron densily for a lJ orbilatlics W<:ll under !hose or the
)s nnd )p and. by extension, even more so Ihose ot the 4s and 4p orbi1Dis.
"'For smoaer clfec1s in lhc tigluer elements, sec PyykkCi. P.
1988. 88. S63-594.
<40
RCICJI!l that one of the differences ot rclluivi lic orbiWI4 from 1hc nonrclnlivi51ic ones Ihoi we are
accus1omcd to handli"'! is lhat the orbilals ot o given voluc ot I an not dqcner:ue: The flpm orbi1ol
below the flp)/1.
a..
41 Jl!rgel\'len,
C. K. Z. Am1'1(. Allg. Chtm. 1986, 540/541. 91-105.
"' The cxpcrimcrual values or atomic electron ulfonities have been reviewed ond ploned os periodic
funCiions. Chen. E. C. M.; Wentwocth, W. E. J.
EJuc. 1975, S2, 486.
Periodic Anomalies of the Nonmetals and Posttransition Metals
881
tions. one wonders why the

were formulated as they were originally. The answer
seems to lie in the lack of data available until recently; most of the good dam were for
familiar elements. such as the alkali metals and the halogens. For these maingroup
elements. with the exception of the lower electron affinity of fluorine resulting from
electron-electron repulsion (and parulleled by oxygen and nitrogen), the rules work
fairly well: however. Ihe poorer shielding d and f electrons upset the simple picture.
For the transition metals. higher ionization energies with increasing atomic number in
a group are the mil' . not the exception. As we have seen in the preceding discussion.
this carries over somewhat into the posttransition
C>lusing some of the
problems associated with families IliA (13) and IVA (14).
The increased ionization energies of the heavier transition metals should not be
unexpected by anyone who has hud u modicum of
experience with any of
these elements. Although none of the coinage metals is very reactive. gold has a welldese rved reputation for being less reactive than copper or silver:J iron. cobalt. and
nickel rust and corrode. but osmium. iridium. and platinum are noble and unreactive
and therefore are used in jewelry; platinum wires are the material of .::hoice for llame
tests without contamination: and one gene rates hydrogen with :tine and simple acids.
not with mercury.
Although the increased electron affinity associated with the heavier elements
usually manifests itself only indirectly (via electronegativity. etc.). it is directly responsible for the fact that cesium au ride. Cs .. Au- . is an ionic salt rathcrthan an alloy.
Both the: increused ioni:tation energy and increased electron affinity in these elements
result from relativistic effects .
We have seen the use of macrocyclic ligands to aid in the isolation of auritle salts
(Chapter 12). The characterization of this unusual oxidation state, both in
[Cs!C222) ]Au and CsAu. was accompUshed by the use of photoelectron spectroscopy
(Chapter 5). When the binding energy of gold d electrons is plotted as a function of the
formal oxidation state of gold (0. +I. + 2. + 3). a straight line is obtained (Fig. !8.81.
The fact t hat CsAu lies on this line at a point corresponding to an oxidarion state of - l
is good evidence for the formation of the auride. Au- . ion...
In the same way. the tY?Au Mossbauer
ofCsAu is very similarto that of
[CstC22))+ Au - !Chapter 121. indiC<lting that the Au - anion is prcs.:nt in both I Fig.
Since the
effect is a nudear one. it is very sensitive to electron
density at the nucleus and therefore to both atomic charge and .<
Gul<l cxhihits other interes ting
For example some AU( I) compounds
with an expected coordimtion number of two (Chapter 12) and 11 filled core of SJIO
The tqend of aq11u r.s:ia seems to pcrsi.<l even in the absence or sludcnl conlacl with this powuful
elixir. Howe..,r. Dtlmimtion for its chcmic:d reactivity is usuutly mi<plncc<l. Thermodynamicully. it
can be no lrOflller 11n oxidizing 3gent 1ha1 nitric: aci<l iuctf. h is the
allility of the soCt
chloride ionsunlhe soCtAu1 ion that allows Au- AuCI; tobeeffccte<lat " - t .OO V. Ralher
more a.'llonishins is the fuel !hut
intern.:tion of vrry suft r- ions cause. the reL'IIively
innocUOU< tincture ol iodine !foond in mllnY mot!icine cubinco.) to dissolve metallic sold readily
!Nululo. Y. J . Cllcm. Srn:., C/rcm. Common. 1992,
44 Kno.'chl. J.: Fi..:ho.'1'. R.; Ovatlof. H.; Hen.<d, F. J . Chcm. S<X Clrcm. C<>mm11n. 19'78, 90$-906.
. , O..tchclor. R. J.: Bircl>all. T.; Bum . R. C. lntlfl{. ChMo. t91!6 . .23. 20()9-.:!01$ .
..., Eb$worth, E. A. V.; Rankin. D. W. H.; Crodock. S.
Mrtlwnb in lltOIJ(unic Cltcmi.rrry.
2nd cd.; CRC: Boca Ralon. FL. t99t; Ch:lfller 7.
+J
Et,
/ P,
fH
8rAu-Au8t-[
[
+2
El,
ic
,.P,
<[" f"
.;
Au
+I
Et,
A -- -
El,
0
81
86
82
87
lllcV
Blndlna 11<11Y
-r
or
Fig. 18.8 Binding

or the Au 14hd levels &old atoms in v:uioos oxi&lion Slaks.
thai the value ror RbAu and CsAu corresponds to that expect..d ror a - I oxidation
[From Knht, J.; Fischer, R. ; Ovtrhor, H.:
F. J.
Soc., Cht'm.
Commrm. 1971.906. Rcproduc..d with permission. !
Fig. 18.9
comparison or
IM chcmicullihiOs in IM
""Au MOssbaucr SptCIr.> of
CsAu and [Cs(C222ll+ Au- .
( From Batchdor. R. J .;
Birchall. T . ; Bums. R. C .
ln"''/. ch...... 1986. 15.
2009-201$.
with permission .J
-10.0
Vdorily (.,..::!)
Periodic Anomoli.. of the Nonmetals and Posllranition Met als
883
lb)
( U}
Fig. 18.10 Two examples of Auii)-Au(l) inlerolCtions. (a) lntrumolecular. Au-Au a 300
pm: tbl lmcrmoiecular. Au-Au )4-1 pm.
Table t8.3 for
of compounds.
!From Schmidbaur. H.: Gtor. W.: Mull. G. Ant<",.., Chrm. /111 . Ed.
1988. !7.
Schmidbaur. H. : Weidcnhaler. G.: Slcigelmilnn. 0 .: Mukr. C . Chrr11. Dcr. 1990. I!J.
Repro.Juc,c d with permission. !
electrons. neverthc:les.< <ho>W

we:tk Au-Au interactions.? For example the
Au-Au distun.:cs in a
of compoun..ls like those shown in Fig. 18.1 0 are given in
Table 18.5. Th.:,.;: distan.:c:s are at or b.!low the expected van dcr Waals toolacts of
aboul JSO pm CTuble 8. 11 and they arc indicative 0( some weak booding in these
compounds.
h has been eslimutcd tha t tho: cno:rgy of the AuCil-Au(J) imcr.tction is about 30 kJ
mor-. which is about the 11rdcr of mugnitudo: of a
bond and the rcsulls are
similar. In some c:ISe, the two gold
arc in the ,arne
and cause ring
formation ! Fig. lli. IOaJ; in other cases tht: Au- Au intemction causes two molecules to
d ime rizc: (Fig. 18. 1llbl.
In addition to I he Aut ll-Airl () bond,, tho:re are ' imilar ime ractions he tween
atums that are a1 congener< of [e.g..
I."' hi lsoelcctronic whh [e.g.
or
Table 18.5
Some .....,pies ol
Au(I)-AuJI) inreroclions or
leu lhon lhe peeled
cliSionce of van der Woalo
contocts
Compound
itNCJ.C.S.Auj; Mc)P;;,.CcPI'h:AuCil: (Fla. II!. IOaJ

(PhAsCCH.PI'h.Au.CI. )J,
(Fig. IS. lObi
lnlro- or
intermolecular bond
Au-Au Jpm)
-------'"--'-
tmralntrn-
'179.6"
300.()1>
lnler
Inter
344.()<1
Sec FootllOIC 4711.

Sec Fooii\Oio 47(hl.
r
S..'C Foolr.llt
Sec f ooi!WIC
n 1.31 Kiwi. N. 1.: W;src. S.: Fxklc:r. J . P.. Jr. INJ'JC. ('h..,.., t9119. 28. )579-JSMll. lht Schmalbour. H .;
Cnd'. W.: MUller. G. An..:...,., Cltrm. lnr. EJ. &..:1. 19M. ?7. 417-419. tel Bolch, A. L: fllr1ll. E. Y.:
Olm'le:XI. M. ,\1. J. Am. CM111 .'itlt". t99t. 112, 31KI-SIIlf. 11.11 Schmidllcllu-. H.: Wcitlcnhillcr. C.;
Sl<i!;clmann. 0 .:
G. C.rm. Dn-. lf'}Q. Ill, 2liS-:!!17.
.. Wq. S.: f :o.:kkr. J. P.. Jr : e:wt.on. T. F. Orstollltmrtullin 1990. 9, 19'7l-t97S.
.. Wang. S.; f'.-:k..,., J. P.. Jr. Dr7f1t1J"'rlllllics l9H, 9, tll-113: Mtu Cf)'Siollutr. 1990. C/6.
884
18 Periodicity
c) isoelectronic plus un iner1 pair with (e.g., 11(1), Pb(II))'O the gold(l) atom . Some
examples ure listed in Table 18.6. The number of these bonds is limited, but the
subject is still a very new one.
The general tendency for atoms (including ot her gold atoms) to exhibit greater
than expected valences toward gold atoms is often termed auropltiliciry. This is a
useful descriptive name for a bonding behavior that is not completely understood. It
appears to result from relativistic effects and the fact that the gold SJIOelectrons do
not act as ' 'good" core electrons but mix with low lying excited sta tes ..SI To rationalize. if not truly explain. one can consider promotion or electrons from the Sd 10
configuration and their involvement in the bonding.
Schmidbaur's group$2 has synthesized some gold(l) compounds with unusual
coordination numbers for small nonmetals. For example, the "hedgehog cation,"
(C(AuPR)>,;f , has carbon with the unusual covalency of six (Fig. 18. 11). While
carbon has no low energy d orbitals, there is
to prevent it from forming a.,.(2s}
and t 1,(2p) MOs and forming three-center bonds. So why should it do so in this
compound and never in "organic chemistry"? Ordinarily the better overlap of
hybridized SP'' carbon orbitals ensures carbon's tetracovalency. Perhaps the possibility of a dozen Au(I)- Au(l} aurophilic bonds could provide another 300-400 kJ
mot- . commensurate with the eneriY or a C-C bond, compensating for weaker
C-Au bonding.
Alternation o f
Electronegativities
in the Heavier
Nonmetals
We have seen above the unusual properties of the nonmetals following the first row of
transition metals. This is usually described as "a reluctance to exhibit maximum
oxid:nion state: but it may also be stated in terms ofan
electroMgutivity in
tlrf.'se el<'mcnts .') Indeed. gallium. germanium. arsenic and perhaps selenium seem to
have higher electronegativities than their liahter congeners.
In the same way, it has been sugsested that the heavier member of each family,
thallium. lead. perhaps bismuth, has a greater electroneg.ativity than its lighter con-
Tobie 18.6
Some fu rlher eompiM of
Group IB (11) metol-metol
inleroctiom
C""'P"""d
Agt, Agl
Aut, Hgll
(AcCH2 P(S)Ph2 }z
Au(CH: P!S)Ph2)z Hg
IC1AuP!SlPh 2CH, I2Hg
Au(CH,P!S)Ph,J,TI
(Au(CH1 P(SJPh2) 1)zPb
Au. Hgll
Au, Til
Au. J>bll
299.()o
308.S
331.0, 336.1h.c
295.9-1
289.6, 296.3.<1
See Footnote 48.

h
Sec Footnocc 49.
There uc two Au-Mz iNenc:tions per moltculc.

J
Sec Foolnolc 50.
10 Wng. S. ; Qorzoo, C.; Kina. C.; Wal\ll, J .C.; F:>ekkr. J. P. Jr. Jnurtf. Ch<vn. tts9. 16. 4611-<4629.
" Jansen. M. An}lnt'.
11'11. Ed. 111(1. 1'*7. 26. 10911-tttO. Rosdl. N.; C&lirc, A.; Ells. D. E .;
Sclunillb:>ur. H. lbiJ. 1,.,,18, llS7-t)S9. PyytkO, P. ; ZJlroo. Y. Ibid. 199t, JO. 6Q.J-605.
Schatooum. F.; Grolmann, A.; Hllbtt, B.; Kr1l&er. C.: Selwnidbaur. H. A/Wnr. C/,..m. lm. EJ.
Elvlf. t988. 21. t$44- IS46. Scbcrbaum. F.: Groh,_. A.; MOller. G.: Sdunidbour. H. Ibid. 1m.
18. ol6l-165. Stcigelmann. 0 . : BmiiiSer, P. ; Schmidbaur, H. /bid. t,., 29, 099-t400.
" Indeed. in many ways, tllese statements are equivalent. Sec Problan 18.17.
Problems
885
fig. 18.11 Structure of the ''hol1:hoa' ' cfocation. ((Ph,PAui.CJ 1 . The inferred At>-Au
bonds are 1101 shown. [From Seherbsum. F .; Grohrnunn, A.; Huber. B.; Krii1:r. C.;
Schmldbaur. H. All,rC'W.
lnl. EJ. Engl. 19118. 27. 1.544- l$46. Reproduced with
pcrmission.J
gener, indium, tin. and antimony. When first propOsed the explanation resled on the
lanthanide contmction acling on lhese elemenls. We now know that relativistic effects
for these clements are at least as important as the lanthanide contraclion and
a
better way of
!he premise is thul all of the elemenls from about platinum on
(there is no shurp . demarcation. of course) are more electronegative than would
oth.:rwise be ex pected.
Conclusion
Problems
The periodic chart is the inorganic chemist's single most powerful weapon when faced
with the problem of relating the physical and chemical properties of over 100 elements. In addition to knowing the general trends painted in broad brush strokes by the
simple rules. the adept chemist should know something of the "fine structure" that is
at the heart or making inorganic chemistry diverse and fascinating.
18.1 Compare Figs. 16.36 and 16.37. The Wft'crcncc in P-0 bond
in P.o,. is ISS 141 .. 17 pm (lt,J, but the difference in !he P-S bonds in P.S,0 is onl y 209 - 196
t 3 pm (6r.). Explain.
18.2 With reprd to nude;u- enslnecring. the sepnnlion of zirccnium and hufnium has been of
considernble inluest be<:ause or the tow neutron CIOOIS section of Wconium and the hish
neutron cross section of hafnium. Unfonunatcly. the SCp:u'1ltion of these two elcmcniS is
perllaps the most difficult of any pair of clements. Expt.oin why.
886
18 Periodicity
18.3 C:>r bcln tetrachloride is inc:n tow.1rds water but boron trichloride hydrolyzes in moist air.
Suggest a reason.
18.4 Below
some conclusions that an average general chemis(ry student (cenainly not
you!) might have after reading about the: periodic table in a general chemistry textbook
written by avc:rase authors (not us!). Please rewrite each stau:mc:nt to clarify possible
misconceptions (if any).
o. Electron affinities increase toward the upper right of the periodic table.
b. Ionization enc:rgies decrease toward the bottom of the sable.
c. Atomic r.Ldii increase toward the boatom or the table.

d. Atomic radii decrease toward the right of the table.
Elc:ctronegmivity decreases toward l he left and toward the boltom of the anble.
111.5 Galium dichloride:. GaCI1 is a diamagnetic compound that conducts electricity when
fused. Suggest a structure.
111.6 If a major breakthrough in nuclear synthesis were achieved. two dements 1ha1 :ue hoped
ror are those with atomic numbers t 14 and 164. both co"'eners of lead. Look at the
extended periodic table in Chapter 14 and suggest prOpenies (such as stable oxidation
states) for these two elements. How do you suppose their electroneg:nivities will compare
with those of the other Group IVA t14) elements?'-'
18.7 The smaU F - S -F bclnd angles in F,SsN can be rati0n3lized by

u. Bent's rule
b. G illespie.type VSEPR rules

Bent bonds
Discuss each and explain their usefulness (or lack thereof) in the present case.
18.8 Either look up the anicle by Chen and Wentwonfi>S or plot the electron affinities from
Tool.: 2..5 onto a periodic chart. DiscUS$ the reasons for the "exc.:ptions" that you
obs<!rve.
IR.9 Write the first ionization energies from Table 2.3 on a periodic chan. Discuss the reasons
for the: "exceptionS" that you observe:.
18.10 On p:oge 863 the statement is rather aually made that "R;:G<:. R,Sn. and R,Ph exist as
diamagnetic monomers in wlution ... What experiments must an inorganic chemist rerfonn to substantiate these
tR.It T he compound R.Sn, shown on puge R63 is diumagncaic . Ornw outahe most
electronic structure for it. and compare it with the geometric structure. Discuss.
IR.Il Lithium carbonate is often administered ornly in the tre-dtment of
or depression or
hoth. From wh:ol you have learned of the di:IJ!un:t relationships in the: periodic chan.
predict one possible
side effect of lithiu m therapy.
1ft. tl Zinc is a much more n:activc: mc:rulahan c:ldmium. as expected from the: discussion on
877-879. Yet bt>lh an: used to protect iron from rusting. How is this possible?
18.14 Sodium hypophosphitc, NaH,PO,. has been suscested as a replocemc:nt of sodium nitrite,
NaN02 , as a mc:at prcserv.llive to prevent hotulism. Dmw the structure of each
"'See Sa\borg, G . T. J .
Etf. 1969. 46. 626; Kutz, J. J.; Morns. 1.. R.; Se-Jborg. G . T. In TI.Ciwmittry of tit<' Aclinltf<' Elmll!nts; Katz. J. J.; Morss. L. R.; Senlx>rg. G. T.. Eds.; Chupmun ond
Hnll: New York. 1986. See alsu Footnote )I .
Footnote 42.
"'See Footnote 11.
Problems
887
18.15 The simplest relationship bel ween elecuorteptivity untl dipole moments Is" linear
'J"he ar eater the difference in electrorcgutivity. the srcuter the dipole. How con
reconcile this with the N-0 und P-0 dipoles cited in this chupla" !page 86'\lt"!
)'W
18.16 The P. molecule in while phosphonJS has cxlrcnlcly

bonds: The b<>nd :\llglcs in
the TJ molecule ..-e only 1>0'. Therefore the bonds ore wcok, only 20 1 k.J mol"' fOt" e.a ch
one. The toiUI bond cncrn o( two moles of P: t962 k.J. Appendix El is
kJ le,;s Ihun that
or one mole of P.11 206 k.J , Appendix El. In contrust , the total bond energy of lwo moles
o( N: has been calculated" to be 777 k.J areotcr thnn that of ore mole: of N. Ia hypolhclicnl
w ith P.).
IC!r.lhedral molecule:
a. Explain the disp;ority
rnolc:cules.
o( bond e nergies o( 1hesc isoclc:clfonic
and i><lSifUCIUf':ll
b. If you nm/d manufncture N 4 und keep 11 as u mctustuble malerinl, CIIJ1 you think of a ny
uses for if!
UU7 Footnote SJ sugests that a reluclllncc to exhib;t maximum uilbtion st ale moy be
to"" iocren..< dl clectronegnuvily in 1hc
e lem<!n,.. Dis.:u<s.
18. 18 Of the five d:ua poi111s in Fia. 18.8. that of AuCH , Et:PCH ,AuCH, Et:PCH: lit> JTOO<t
poorly. SutU:est a pos.ible reason.
Assumingohot CsAu is ionic . whal is its mo" probuble
formation for io.
E"irnate an
of
18.20 Two vuriablc:s :alfectinl: the isum<r >l!ifl ill MU..<b;tucr spe.:ti'\N:opy :trc the < clloJ/Xtcr o(
the orbilul involw<!d a nd lh<! panbl c h:o,.,.., oln the
hcinr ..tu.Jic.J. E\pbin this
phenurncnon
i.e .. in tcrnt' uf huw the>C IWII ljllllntlli<' .JfTcct 1hc
oknsity ut the
18.21 Despite the holf..:.:nlury hil'!u ry of Sc:ohlli'!:'S hypoth.:.i> wi th rcSfl<'Cltu the

uf
the lanlh>nl<k-< nd ;octini<J.:, in the p<r1\ldi.: a:.hlc. tmtny l>cn.:h
J>I'<>Cc<l\1 <ue>:cssI\IUy with the
tht ur.nium ;,. : cont;cncr uf tTWI)I>oknum >nd tung
stcn. Oucs
inJi.::ue lh:u Scb.lf
\>ro1rc That the
.:hcmi<l<
wrong?
[)jscus"'.
18.22 How m:tny p;1rJIIcls

((AuPI'h,J,q' lf.it;s.
13.!..1
ynu Rntl bct,.cen IFc,JCOJ.-CI'

tS.2tbJ and
und
'""' conlril>ntc to the unusual hc-.ocooniin:ue
the dectrur*: .ntJ 'tructural
tn\uhal in th.:
(18.56)
" Lee. T. J.; IOcr. J . E. J. c:Nm. Ph.u. 1991. 9#, 121$-12::!1.
888
18 Periodicity
111.24 Discuss any similarities :llld dlfTerences between Eq. 18.S6 above and the behavior of
"Pt(pop)" culalysu in ChOI)tCS' 15.
18.25 From the discussions in this c.hapter and those in Chaptc:o- 14. plus any further data you
lind in standard reference woc1cs, write u Jt>urnul of Chrmicul EJucution-typc article
entitled: "Alchemy revc:o-sed: The remarkable chemistry oltuming BOld inlo even more
interestina subslllllCes!",.
" Lest we get carried aw'.t)' by the rlletoric. this would simp)' be a review arock of aofd chemiWy
with the provocative lfltsis that il hu u more varied and intereslina chemistry than a.,y o&hodcment.
Chapter
19
The Inorganic
Chemistry of
Biological Systems
The
of life can ul timately be referred to two chemical processes: (I 1 the use
or radiant solar engy to drive chemical reactions that produce oxygen and redua:d
orpnic compounds from caroon dioxide and water. and (2) the oxidat.i on of the
products of ( I) with the production of carbon dioxide, water. and energy. Alternatively ,living organisms have been defined as systems capable of reducing their own
entropy at the expense of their surroundinas (which must gain in entropy}. An
important feature of living systems is thus their unique dependence upon kinetic
stability for their existence. All are thermodynamiclll ly unstable-they would burn up
immediately to carbon dioxide and wate r if the system came to thermodynamic
equilibrium. Life processes depend upon the ability to restrict these thermodynamic
tendencies by cont.rolled kinetics to produce energy as needed. Two important aspects
of life will be of interest to us: (I) the ability to capture solar energy; (2) the ability to
employ catalysts for the controUed release of that energy. Examples of such catalysts
are the enzymes which control the synthesis and degradation of biologically important
molecules. Many enzymes depend upon a metal ion for their activity. Melal-contnining compounds are also important in the process of chemical and energy transfer,
reactions which involve the
of oxygen to the
of oxillotiun and various
rl!\lox reactions resulti ng rrom its use.
Energy Sources
for Life
Nonphotosynthetic
Processes
It may be somewhat surprising that most of the reoctions for obtaining energy for
living systems are basically inorganic . or course. the reactions are mediated and made
possible by complex biochemical systems.
Even though almost all living organisms depend either directly (green plonts) or
indirectly (saprophytes ond animals) upon
to
the energy ofthe
sun, there are a few reactions, relotively unimportant in terms of scale but extremely
I Thc.sc roductiorist clcfnicions Of li(e ale nol mc::lnttO imply
processes 00'
O<prUms aTe
simplislic OC" any the le.ss illleteslins- A sirnilat cldiolilio<t or physics ard cheiTisary ITi8f>l b< -the
Sludy or the int.enctioos or mallei' :wl enctJY" None or these definiaiorw hillls at the fascinlltio4 of
some ofthe prctiems presented by these brancbes of science.
890
19 The Inorganic Chemiotry of Bialagical
interesling in terms of chemistry, utilizing ifiOI'ganic sources of energy. Even these

may be indirectly dependent upon photosynthesis. since it is believed thai all free
oxygen on eanh has been formed by photosynthesis.
Chemolilhotrophicl bacteria obtain energy from various sources. For example,
iron bu,terio produce energy by the oxidation of iron( II) compounds:
2Fe2+
...!2!...
+ energy
(19.1)
Nilrif:ving bacluia are of two types, \ltilizinc ammonia and nitrile ion as nutriments:
2NHl -.2.. 2NO! + 3H20 + energy
(19.2)
N01 __!2!.. NO) + energy
(19 .3)
Though they are photolilhotrophs (Gr. plwtos, "light") and thus more closely related
to the chemistry of normal photosynthesis (see pnge 916), the green sulfur hacuria
and the purple sll/fur bucluia are included here to demonstrate the diverse bac!erial
chemislry based on sulfur paralleling !he more common biochemislry involving water
and oxygen. ugh! ene.rgy is used lo split hydrogen sulfide into sulfur, which is stored
in the cells. and hydrogen which forms curtlohydrates, etc., from carbon dioxide.
To return to !he chemolithotrophs, there are species of sulfur bacteria thai obtain
energy from the oxidation of various states of sulf\Jr:
...!!!!... Sa +
8H2 0 + energy
(19..4)
(19.5)
These Iauer reactions are the source of energy for a unique fauna, one completely
isolated from the sun on the ftoor of the ocenns. These ecosystems have been
discovered at cenain rifts in the earth's crust on the ocean's Hoor. where large
amounts of sulfide minerals are spewed fonh from hydrothermal vents.l The sulfide
concentration, principally in the form of hydrogen sulfide, ranges routinely up to
100 11M depending upon the dilution of vent water by surrounding sea water. The H,S
has been shown to be depleted, along with Oz. in the midst of t he aggregated
organisms, and it is the energetic basis of these communi ties. The sulfide is oxidized
by bacteria as shown above. II is of considerable interest that the enzymes, mechaand products of this chemical ly driven synthesis are essentially identical to
thtxc of phottxynthesis (page 916). except t hat the source of electrons for the reuuc
lion of water to carbohydrates is sulfurt - Ill rather than photonctivated chlorophyll.
In addition to free-living bacteria, many of the vent animals cont:tin endosymbiotic
bacteria that serve them as primary energy sources as well as the source of reduced
carbon compounds. The parallel between these endosymbionts in rift animals. such as
tube worms, clams, and mussels, and the chloroplusts of plants is striking.s Whether
lllal is, feeding (Gr. tr0plro1) on iiiOI'gOIIIic (Gr. litltos, "xtone"l cho:micals.
'Spi.!ss. F. N., Macdonald, K. C.: Alw.Uer, T.: Bllllnrd. R.: Crrunu. A.; Conlollu, D.: Cox. C.:
Diaz Gat'cia, V. M.: fr.JnChcteau. J.: Guerrera. J.: How!Ons. J.; Haymcn. R.; Hes>lcr, R.: Jureau.
T.: Kastncr. M.: l.ancn. R.: Lllycndyk. 8 .: Macdoupll, J. D.; Miller, S.; Normarl<. W.;On:ull, J .:
C. Sdrncr 1910. 1(11. 1411-14)). Hdcini..,, R.: Fevric:r. J. L.: Pic:d, P.: Sh.nks. W. C . lbiJ.
19St. 2f11. 1433-1444. EdMond, J. M; Von Damm. K. L .; McDull'. R. E.;
C. I. Natuu
(t....JMioff)
1911, 297. 117.
Johnson. K. S.: Beehler. C. L.:

1139-1141.
su-o-Arnold. C.
' Childress. J. J.: Fclbeck. H.; Someto, G. N. Sd. ;tm.
M.; Chiklress. J. J. Sritttcr 1986. ZJI.
am, 256(S), 114-t20.
MetaUoporphyrins one! Respiration
891
this parallelism results from an adaptation of the cycle from photosynthetic bacteria.
or whether these chemolithotrophic bacteria ::are pos.sibly ancestral to photosynthetic
phylogenetic problem-which came first. the chicken
organisms presents the
or the egg? The entire community. including predator species such as crabs. is entirely
independent of photosynthesis except for the use of by-product dioxygen. There is
even evidence that some of the animals such as gutless clams can metabolize hydrogen
sulfide independenlly. simullaneously detoxifying it and using it as an energy source.6
Metalloporphyrins
and Respiration
Cytochromes
Some of the simplest bioinorganic compounds are the various cytochrornes. In terms
of overall structure and molecular weight they llre <Jnything but simple. However. the
inorganic chemistry of several of them is very simple coordination and re<lox chemistry. The ::active center of the cy10chromes is the lieme group. II consists of ::a
porphyrin ring chelated to an iron atom. The porphyrin ring consists of a rnacrocyclic
pyrrole system with conjugated double bonds (Fig. 19. 1) and various groups at ruched
to the perimeter. We shall not be concerned with the nature ::and variety of these
substituenls except 10 nole that by their electron-donating or e.lectroD-withdra""ing
ability they can .. tune'' the
molecular orbitals of the complex nO<! thus
vary its re<lox properties. The porphyrin can accept two hydrogen ions to form the +:!
di::acid or don::ate two protons und become the -2 dianion. It is in the lulter form that
the porphyrins complex with metal ions, usually tlipositive, to form metalloporphyrin
complexes.
From the covalent bon<l radii (Table 8 .1) we can estimate that a bond between ::a
nitrogen atom and an atom 0( the first
ilion series should be about 200 pm long.
The size of the .. hole.. in the center of the porphyrin ring is ideal for ::accommodating
metals of the first transirion series (Fig. 19. 1bl. The porphyrin system is fairly rigid.
,,,
Fig. 19.1 Ia I The porphyrin molecule. Porphyrin.' have substituo:nts a1 the eight pyrrotc
positi..n.. (bl A ''best'' set cl p-ramctcrs for an ..3vcra!ll='' porphyrin sk<-lc:ton. Distance in
pm. (From Fleischer. E. 8 . AC'C'. Chrm. Ru. 1970. J. lOS. Reproduced with pcnnission.l
Powell. M. A.; Somero. G . N. Sc;,,u 1986, ZJJ, S63.
&92
19 TM l natganic: Chemistry of Biological Syslms
ond the
bond distance does not vary greutly from 193-196 pm in nickel
porphyrins to 210 pm in high spin iron(ll) porphyrins. The rigidity of the ring derives
from the delocalization of the .,. electrons in the pyrrole rings. Nevertheless. if the
metal atom is too small. as in nickel porphyrinates. the ring becomes ruffled to allow
a pproach of the nitrogen atoms to the metal. At Ihe o ther extreme. if the metal
atom is too large . il cannot Iii into the ho le and sits above the ring which also becomes
domed (see page 903).
'The order of stability of complexes of porphyrins with + 2 metal ions is that
expected on the basis of the Irving- Williams series (see Chapter 9), except thai the
square planar ligand favors the d 8 configuration o(
The order is
.. > Cu2+ >
2
Co > Fe2+ > Zn1 +. The kinetics of formation of these metalloporphyrins has also
been measured and found lobe in the order Cul > COJ+ > feH >
If this
order holds in biological systems. it ,soses interesting questions related to the much
greater abundance of iron porphyrins (see below). What might have been the implicalioos for the origin and evolution of biological systems if the natural abundance of iron
were not over a thousandfold greater than those of cobalt and copper?
The porphyrin ring or modifications or it are important in several quite different
biological processes. The reason for the importance or porphyrin complexes in a
variety of biological systems is probably twofold: ( I ) They are biologically accessible
compounds whose f'unct.ions can be varied by changing the metal, its oxidation stale.
or the nature or the orpnic subslituents on the porphyrin structure; (2) it is a general
principle thai evolution tends to proceed by modifying structures and functions that
are already pre.s enl in an organism rather than producing new ones de novo.
The heme group is a porphyrin ring with an iron atom allhe center (fig. 19.2). The
oxidation stale' or the iron may be either + 2 or +'3, and the importance of the
0
'\.::-o
- .0
"'-cY
Cll,
,jc,
R1 a CH = CH!
CH,
I -
CH
Hcmo:A.
5"',
R, c ,.H.,OH
I .
_......cH .,_
H.:n>< B
'
c- "
II
Cll
R1 - C
C- N
'
/
f-.:
/
-......_
s-c
'
R 1 R:Ci t == CU!
'
R: Cll =Cfl:
\\
I
CH
N=C
\-"
I
CH)
C-CH
R 1 CCH I == O
R,
Fig. 19 .2 The heme aroup: Type A

are found in cytoc:hrome o; Type 8 hemes are
found in hem<>globin. myoslobin, peroxidase. und cyloc:hromc h; Type C hemc:s are found in
cytochrome c; chlorobCfl)c is found in chlorocruorin.
7 Bishop. D. G .; Reed, M. L
Pl10tobM. I!n. 1916, 1, I .
rden 10 the neutl'lll(lt'OUp conlainina Fctlll. either

oo- in u protein. When the
lsoblcd heme u oxidized 10 FctUI). there will be a IICl
charc arol osn associwed. c:oonltnated :Won. often tht c hloriolt ion. When oxicflltd. t he term
ilc ull!llicd.
hemin chloride.
lone thouj;IIIIO be .. hemin hydroxide." is :x:IWII!y a 1>oOXO dimo:r tsee page 1196) .
lllo:
MetalloporphyriM and Respiration
893
cytochromes lies in their a bility to act as redox intermediates in electron transfer.

They are present not only in the chloroplasts for photosynthesis but also in mi tochondria to take part in the reverse process of respiration.
The heme group in cytochrome c has a polypeptide chain attached and
around it (Fig. 19.3). This chain contains a variable number of amino acids, ranging
from 103 in some fish and 104 in o ther fish and terrestrial vertebrates to 112 in some
green plants. A nitrogen atom from a histidine segment and a sulfur atom from a
methionine segment of this chain are coordinated to the firth and sixth coordination
sites of the iron atom.9 Thus, unlike the iron in hemoglobin and myoglobin (see
below). there is no position for further coordination. Cytochrome c therefore cannot
react by simple coordination but must react indirectly by an electron transfer mechaIt can reduce the dioxygen and trunsmit its oxidizing power towards the burning
of food and release of energy in respiration (the reverse process to complement
photosynthesis). The importance of cytochrome c in photosynthesis and
indicates that it is probably one of the oldest (in terms of evolutionary hi tory) of the
chemicals involved in biologicul processes. An interesting "family tree" of t he evolution of living organisms can be constructed from the d ifferences in amino acid sequences in the peptide chains between the various types of cytochrome c found. for
example. in yeasts, higher plants. insects, and humans. Despite these differences,
however, it should be noted that cytochrome c is evolutionarily conservative.
chrome c from any eucaryotic species will react with the cytochrome oxidase of any
other eucaryotic species, plant or animal. thoU)1 at reduced r.ues. to
There is quite a variety of cytochromes. most of which have not been as well
characterized as cytochrome c. Depending upon the ligands present. the redox potential of a given cytochrome can be tailored to meet the specific need in the electron
transfer scheme. whether in photosynthesis or in respiration. The potentials are such
that the electron flow is b-+ c- u- 0 2 At least some of the u type (cytochrome c
oxidase) are capable of binding dioxygen molecules and reducing them. They are thus
the last link in the respir.uory chain of electrons flowing from reduced foodstuffs to
oxygen. Therefore. they must be five coordinate (in the absence of
in contrast to
cytochrome c. They are responsible for the unusually severe and rapid toxicity of the
cyanide ion. CN - . The Iauer binds strongly to the sillth position and stabilizes the
Fe(lll) to such an extent that it can no longer be readily reduced and take part in
the electron shultle. The cyanide ion is isocl,ctronic with
carbon monoxide
molecule and it might be
thut it cou ld bind tightly to hemoglobin
CO.
However. cyanide binds well only to Fe( II I) hemoglobin (mcthemoglobinllJ, an aberrant form usually present only in small quantities. Cyanide poisoning is thus not the
result of lack of hemoglobin function (as is CO poisoning). In fact. the standard
treatment for cyanide poisoning is inhalation of amyl nitrite or injection of sodium
(see page 907). The IaUer.
nitrite to oxidize some of the hemoglobin to
Forthcc:omplele structurcsoHerrocytociYomc(" !Fe!), secTok3nO. T.; Trus, B. L.: Mandel . N .;

MM<Icl, G. ; K:JIIni, 0 . 8 .; Swanoon, R. ; Oidtcnon, R. E. J . Bioi. Chmr. t977,
T76-71.S.
m.
1... DilttmiiiT)', lfdcd.;

New Yorit. 198t; pp )28-):!9. Dicknon. R. E. Sri.
J4mtr. t97'_ 2215141 pp 58-72.. UcoryOii(" cells have thOr DNA in t.ruo nudci. as opposed 10
cells (baclcria and bluc:-pecn olpc) which do Mt.
"Tile prefix_,_ is liSN to slpiry thatlht iron atom, - d y in the +2 oidation slale. lm been
to + ).
to Sec Strycr.
0>
-o
..
-o
....
i!.
"
9
i.
!
..
i5'
0
'.
"2..
-r
..:1
Fig. 19.3 (a) Schemalic view or

heme croup Is viewed edge on, with the iron atom (large black atonl)
cuuroinated to a sulf'ur atom from ;r nrclhiunin.: rcillue and a nilrogen atom from a histidine residue. (b) Slereoview urI he
cy1uchron1e c n1olecule. Each numb.:r represents an an1ino Mcid in Ihe protein chain. Note the complete cooroination sphere
ur the iron atom as well as the
afToroell by Ihe encircling protein chains. (Counesy orR. F.. Dickerson and from
Takano, T.; Trus, D. l .. ; Mandel, N.; Mand"l, G.; Kallai, 0 . 0 .; Swanson. R.; llickcrson, R. E. J. Bioi. Chtm. 1977,2$2,
771>-785. Reproduced wilh permishn.(
Oioxygen Binding, Transport, and Utilization
895
allhough useless for d ioxygen transport. binds cyanide even more lightly than hellll>globin or cylochrome oxidase nnd removes it from the system. tz
The
of cytochrome c o xidase is not known completely. II contains two
heme groups of the cytoch rome type (n and a,) and two copper atoms (CuA and Cu 8 ).
When the
Fe(ll ) oxidase is trea ted wit h carbon monoxide. the ul moiety binds
it and g ives a myoclobio-carbon monoxide-like s pect rum. The a site does not bind
carbon monoxide , indicating a six-coordinate, cytochromel.'like structure. The Oltidized. Fe(lll) form binds cyanide at al, but not at u. supporting this interprewtion.
(Metmyoglobin and methemoglobin will a lso bind cyanide, but cytochrome c will noc.)
The EPR spectra of iron and copper show that al and C u 0
antiferromagnetically
coupled. and EXAFS (see page 91 31 me"olSurements indicolte th<st these Fe and Cu
atoms are a bout 370 pm apart. compa tible with a sulfide bridge. The electron now is
probably: ')
119.6)
Dioxygen Binding,
Transport, and
Utilization
The Interaction
betw-n Heme
and Dioxygen
While all or the biochemical uses of the heme group ;we obviously important . the one
that has pemaps anracted the most :lllention
of its central biolo{!ical role and
its intricate chemistry is the bindinl) o( the dioxygen molecule. 0!. This has been
mentioned briefly above with fCG'lrll to the bindinte :.nd reduction of dioxygen by
cytochrome oxidase. Before this step occurs. vertebrates" have already utilized two
other heme-containing proteins: Hcrnoclobin picks up the J io xygen from the lungs or
gills :.nd tmnspons it to lhc
it is stored by myoglobin. The function of
hemoglobin in the red blood ce lls is obvious . th:tt of myoglobin is more subtle . Besides
being a simple reposittry for dio'<ygen , it also
a dioltygcn res erve 3g;linst
which the organism can draw luring increas ed utelabolism or oxygen
Other suggested functions inclulle faciliuuion
diollygcn now within the cell a nd a
of the panial
within the cell in
to
or decreasing oxygen supply , th
the
ide.
Oioxygcn is far from a typic:lli:;and . It p robably
nitrnsyl. and llinit rol!cn
:ha n any
None of these has 3 s ignificant
hl the or h.ln.J . but the
d illerencc t>cllipolc mo ment
twc.:n thc "'oms in CO :end NO
., intcr.1ctinns bee C h:eph:r Ill. Dinitrogcn
lad; lhi
hut may be considered SOfi
with SIIIIIC ':T
a n.J
bonlling
Iron(( I). J". is not a purticularty son mct:l c:ation. but the soften-
or
1!
S.:c ll:lnzlik. R. P. Jn.,..,wtir: Asf'N'll uj'Ohth'J:W<il ,.,J 01):"'tir Chnni.w y: llca<Jcmic: New YOI'k..
1976. p
Oc:hi:li . E t.
CIIMdstty : Allyn & B:oc:on: RO!olnn. 1'177; p 48).
u Sec:
osnidcs on cyaodvomc: uxkb."e in FJ,.,.,m, TrcuufHWI und o.,.,,.ltt:ll Ulill:.utivn: Ho.
Ed.: Ell<c:vic:r Nonh Hobo&!: New Yoot.

Karlin. K.: (iubneh. Y. Pm,r. lnurt. Orm. 19l!7.
J.5. lt0-311.
'There is on exception in cxnain " blOO<IIc""" Antoretic 1\shes (Chllc.'11ocluhyid:.et in which the
metahulism r.< so low unci the OltYCCft !l<llut.lity..., hiall. both
rrum the extrcmcly low water
Jempcr.ui.W'I:S. th:U OXYen c::>rricrs an: rut ncceJ<<ry.
" Divi1111 .....,..x., <UCh a< wh:llc:.< howe 3 wrtte umouno <)( myo'lk>bin in their
which prc:sum:ably Ctl:lhles them "' remain submerJ'(I (or ctendcd
or lime .
.. S Cole. R. P. Scr<n
116,
896
19 The Inorganic Chemistry of Bialogical SJslems
ing" (symbiotic) action ol the telr.lpyrrole ring system probably facililates dioxygen
binding. Note that the heme group binds the truly soft ligand carton monoxide even
more tighUy, resulting in potentially lethal carbon monoxide poisoning.l7
is another potentiaUy fatal fiaw in the binding of dioxygen by
However,
heme: irreversible oxidation. If free heme in aqueous solution is exposed to dioxygen,
it is converted almost immediately into a ..,..oxo dimer known as hematin. The
mechanism or this reaction has been worlced out in detail. IS The reactions are as
follows, where the heme group is symbolized by t he circle about an iron atom. The
first step is the binding of the dioxygen molecule, as in hemoglobin: 19
.o.. --.GU-o
(19.7)
The bound dioxygen can now coordinate to a second

complex:
G"
forming a ..,..peroxo
(19.8)
0-Fc
Cleavage or the peroxo complex results in two molecules of a ferry! complex with the
iron in the + 4 formal oxidation stale:
(19.9)
Finally. attack of the felT}'I complex on anOiher heme results in the form:llion of
hematin:
(19.10)
17 Cart>un monoxide
may be trcaled by lloodina lhe aySitm wilh oxyeen. Nevenhdds. 1he
binding of CO is about SOO limes 111"01\iCr lll:ln the bindina of
h could be worse. Carboo
monoxi<lc binds even ...,...
(by obout 1wo orders of ITilSI'hlkkl 10 rrec heme. n.c stcric
hindnncc :.bout lhc heme in hcmQglobln and myq;Sobin rn11y ravor the
over lhc toptimllly)
linear carbon monoxide. (Sir)'..-. L. Diodlmltr)'. 2nd eel.: A'ccman: New York. 1981: p S4.)
Balch. A. L. ; Olan. Y.W. : Chctls, R. J.; u Mar. G. N. : utao<-Grazyn.\ki, L.; Renner. M. W. J.

Am. Chrm. Soc.
106. 1779-nas: PcnncrHahn. J.
K. S.: McMurry, T. J.: Renner,
M.: &lei>. A. L.: Groves, J. T.; Dawson. J. H.; Hod(I:IOn. K. 0 . Ibid. 1986, JOB. 7819.
"The o>Udalion swcs may occuionaly be lllnbiJIIOUf-lhc :wldoct in Eq. 19.7 may be ronr&llalal as
hemc{tll-<lioXYacn or as heme (rtl)-wpero>Udc. Sec Problem 19.21.
1B
Dioaygeto Binding, Transport, and Utillzation
897
Obviously, living systems have found a way to frumate reactions 19.7-19.10:

otherwise all of the heme would be
as hematin r.llher than shunling
eleclrOns in the cytochromes or carrying dioxygen molecules in oxyhemoglobin (and
storing them in oxymyoglobin). There may be
than one mechanism in effect
here, but certainly the primary one is sll!ric hindrance: The globin part of the molecule
prevents one oxoheme from attacking another heme. This was first illustr.tted over
thirty years ago by embedding the heme group in a polymer matrix that allowed only
restricted access to the iron a tom: The embedded heme will reversibly bind dioxygen.w More recently this same result has been achieved by "picket-fence" hemes and
related compOUnds (Fig. 19.4) that reversibly bind dioxygen21 and not only confirm the
steric hypothesis with regard to the stability of hemoglobin, but allow delailed structural measurements to be made of a heme model compound. Thus the angular or bent
coordination
dioxygen to heme (in hemoglobin and myoglobin) was first indicated
by the s tructure shown in Fig. 19.4 . It has since been confirmed in myoglobin and
hemoglobin (see below).
or
The Binding af
Dlo"Ygen to
Myoglobin
Myoglobin is a protein of molecular weight of about 17,000 with the p rotein chain
containing 153 amino acid residues folded about the singJe heme group (Fig. 19.5).
This restricts access to the iron atom (by a second heme) and reduces t.h e likelihood of
formation of a hematin-like Fe( Ill) dimer. The microenvironment is similar to that in
cytochrome c, but there is no sixth ligand (methionine) to complete the coordination
fig. 19.4 Perspective view o( picket-renee dioxyacn udduct. The

presence of four
different 02 ntoms results from a four-w"y statistical disorder o( the oxyaen
on
different molecules respondinato the X-ray diiTrxtion. (From Collmnn. J. P.: Gagne, R. R.;
Reed, C . A.; Robinson. W. T.: RO<llcy, G. A. /'me. Nml. Mod. Sci. U. S. A. l!n4. 71,
1)16-t329. Rrproduced with permission.)
2D Want. J. H. J. Am. Owm. Soc. lts8. 40. l t6&: Ace-.

11
Ru . 1971. J . 90.
.Jamc:son. G . B.: Molinoro, F. S.: tben. J. A.; Coli"""' J. P.:

J. 1.; Rose. E.: Suslic:k.
K. S. J. Am. CMm. Soc. l.t M, 102, 3224-3237. For review o( steric:llly hin<lcred biomimclic
porphyrins, see Morpn, 8.; Ootphin. D. StTUC't. Donding
1987, 64, I tS.
898
19 Tlte Inorganic Chemist.y of Biolagical Systems
Proltin
chain
(bl
(1)
Fig. 19.5 The myoglobin molecule: (n) the folclloa of 1he polypeplide cllllin ubout the heme
sroup (represented by lhe disk); (b) close-up view
the h.:mc environment. [Modified from
Kendrew. J. C.; Dickerson. R. E .: Strnndbcrc. 8 . E .; Hun. R. 0 .:
0 . R.; Ptlillips.
0 . C.; Shore. V. C.
1960. /8J. 422-477. Reproduced with permission.!
or
sphere 0( the iron atom . Thus Jhere is a sile to which a dioxygen molecule may
reversibly bind .
Note how the differences in structu re between the dioxygeo-binding molecules
(myoglobin, hemoglobin, and cytochrome oxidase) and the electron carriers (various
cytochromcs, including cytochrome oxidase which performs both fu nc tions) correlate
with their specific functions. In myoglobin and hemoglobin the redox beh:!vior- is
re tardec.l. and there is room for the dioxygen molecule to tOOI'dinate without electron
tr.msfer taking place.:!2
Myoglobin contains iron(JI) in the high spn state. lron(ll) is d 6 and, when high
s pin. has a radius of approximately 92 pm in a pseudo-octahedral environment (the
square pyramidal arrangement heme in myoglobin and hemoglobin may be consid
ered an octahedron with the sixth ligand removed), and the iron atom will not fit into
the hole o f the porphyrin ring. The iron( II) a tom thus lies some 42 pm above the plane
of t he nitrogen atoms in the porphyrin ring (see Fig. 19.6). Whe n a dioxygen molecule
binds to the iron(ll) atom, the latter become.\ low spin
(cf. the extremely stable
Co' complexes with 2.46 LFSE). The ionic rJt.lius orJow spin iron! II) with coort.l ination number six is only 75 pm. in contrast with the 92 pm of high s pin iron. Why t.hc
t.lifferen.:c? Recall that in octahedral complexes
orbitals are those aimt!<l at the
ligands. If they contain elec trons. which they llo in the h igh spin case
e;l.
they will repel the ligands as opposed to the low spin case (tt,
which allows
unhindered access 0( the ligant.ls along the coordinate axes. Thus the effective radius
of the iron a tom is
(along the x, y, and z
in the high spin state than in the
low spin state. The result is that the iron a tom shrinks upon spin pairing and drops intu
the hole in the porphyrin ring. All the ligands (including the proximal histidine) are
able to a pproach the iron a tom more closely. The net effect in myoglobin is minimal,
but the process is an important one for the transmL'ISion of dioxygen from the lungs to
the tissues b y hemoglobin. The spin pairing
the normally puramagnctic t.lioxygen
molecule is also of interes t, though often overlooked (see Problem 19.9).
or
or
or
!2
Indeed. lalqlobin has been duttlcd " rn.ost<'Jicd oxiCb>e" IWinlcot>own. C. C.: French. J. K.
/Jiocltrm. Soc. TrtliiS. 1971. J . 1480: Frendl. J. K. : Wintcrboum, C. C.: Cam:ll. R. W.
J.
1978./7J. 19l.
OioiC'(9en lin ding, Tronsport, oncl Utilizotion
fig. 19.6 Close-tiP of the hrme aroup in m)'OI:Iobin and

docs not 1ft: in the plane of the heme StOUP
899
Note !hat the iroo atom
A knowledi)e of the exact molecular arrangement of dioxygen in oxymyoglobin

and oxyhemoclobin has been llesirJble in order to understand the chemistry of
llioxygen transport und storase. Unfonunutely, this has been diffiCult to achieve
because of the high molecular weiGht of tilt molecules and the low resolution of t he X
structures. The structure that has been determined to the greatest
resolution is that of oxyerythrocruorin which
been relinell to a resolution of 1-10
pm.:J The dioxygen is bonded to the iron with an ungle of
und an Fe- 0 bond
length of -l&l prn. Oxymyoglobin !sperm
and oxyhemoglobin thuman,:s
have not been resolved us highly (2111 pm), but the Fe- 0 bond lengths are similar. All
of these are compatible with the more accurate value of 190 pm in the picket-fence
adduct.!<> However. the Fe- 0 - 0 bond
vary considerably. from -115" in
myoglobin to 153" in human hcmoslohin (for more Jemils, sec Table 19.1.
905)
with the m u'it accurntc value heine 13 I" in the mollel picket-fence compound. The
snurcc of the .Sifferences is n<>t cle:tr. but cukul:llions27 indicate that the bond energy
chnngcs but little with bund unglc. :tn<.l so other faculrs such us stcric effects or
hy<.lrogen bonding with a neighboring group coultl be important (Fig. 19.7).
- rso
Erythrocruorin is a form of myC)Il)obin fcltlnd in chironomid mldt;cs (llics). In conerol, the sre:ucr the
.-..olulion Uhc smaller this v.:lluct. the more <lclCurate the )lructur.JI detcrminalio11. IXJt it should be
rc:llizro lhal the n:finemenl or structun: or protein.' cont.,inan, tellS ot' thllllSOnds o( atoms is r...
.,.-,.c complicated thao the !\lmost !'I>Utinc dc:termin:llit>n of stni()IUR:S ol mok:c:u(cs containi111: a few
doz.on moms at mo51. ()(ton :lllsumpli<JN mu." be
with a rcsulli111 shift o(
lhc:
M-o-o bontl analc in crylhroo:ruorin was IXlrncrcd num 171l' (extn.onlin;vy!) to 150" when ueh
BMUmpllons were
rSteit;cm:u>n, W.: Wo:bc:r. E. J. Mttl. Dlol. 1!179. 111, .l09j.
:>e PhiUip;. S. E. V. Nalllu (l.ottdolrl l918,l7J, 247: J. Mr>l. Ditll. IMt. 141, SJI .
:> Shaanan. B.
(LIIfUlott} 1982,296, 68): J . Mul. Diol. 19113, 171. )1.
"' Jameson. G. B.: Rodlcy. C. A.; Robinson. W. T .; CAcne. R. ll; Rcc, C. A.: Coiiii'Dn. J. P. l no<x.
Clwm. 1!178. 17, H$CHIS7.
!J
Z1 Holfii13M, R. : Chen. M. M.L : Thclm. 0 . L lttt"'/. Clll!m. 1977, 16,

l.oew, G. H. J . Am. Otm. Snt:. t977, 911,
Kirchner. R. F.;
900
19The Inorganic Chemistry af Biological Systems
Fig. 19.7 Stereovicw o( superimposed heme environments in oxyhcrnoglobin and

oxym)'081obin. Solid fines denote Hb<}z and dashed lines Mb01 Note the diiJcrenc:e in the
Fe-O t-02 bollll "81Cs and the presumed hydroaen bond (dotted line) 10 the hisridine (His
E7l."[From Shaannn. B. Nuturt (London) 1911,196, 683. Rep<"oduced with pcnnission.)
The Physiology of
Myoglobin and
Hemoglobin
In vertebrates dioxygen enters the blood in the lungs or gillsll where the partial
pressure of dioxygen is relatively high (21% oxygen 0.21 x 1.01 x 10' Pa
(760 mrn Hg) = 2.1 x 10' Pa ( 160 mm Hg)) under ideal conditions; in the lungs with
mixing of inholled and nonexhaled gases. the value is closer to 1.3 x 10' Pa
( 100 mrn Hg). It is then carried by red blood ceUs (Fig. 19.8a) to the tissues where the
partial pressure is considerably lower (cl the order of 2.5 x lo' to 6.5 x lo' Pa (2050 mm Hg)). The reactions are as follows:
Lungs (gills)
TlSsues
Hb + 402
Hb(02)4 + 4Mb -
Hb(02) 4
4Mb(02)
(19.11)
+ Hb
(19.12)
Note that hemoglobin has an ambivalent function: It should bind dioxygen tightly and
carry as much as possible to the tissues, but once there it should, chameleon-like.
relinquish it readily to myoglobin which can store it for oxidation of foodstuffs.
Hemoglobin serves this function admir.ably as shown by Fig. 19.9 : (I) Myoglobin must
have a greuter affinity for dioxygen than hemoglobin in order to effect the transfer of
dioxygen at the cell. (2) The equilibrium constant for the myoglobin-dioxygen complexation is given by the simple equilibrium expression:
K,..t> =
[Mb(O,))
(M'i;j[O;J
(19.13)
If Ihe total amount of myoglobin ([Mb) + (MbOz)) is held constant (as it must be in the
cell) while the concentration of oxygen is varied (in terms o( partial pressure). the
,. Smoll Clfi3Mm Quire no ox)'Ben lr.II\Sport sysrem beyond Aimple
There is a (amity of
M&less lillamanden, the PlelhodONicl:>e, wllidl ,....., neirher aills nor lunas (as adults) and rdy
llpQ1 oxnen exefwlae throo&h the skin and
( .. moolh and throat")
exeJwrce. Some worms und molusb have p-ouins rdwed 10 henqlobin forox)'Btn lra11$pon and
SLonge. Some polyc:hacre worms employ
whidl turns green upon oxyacnation.
Sipmculid wonns and some 01her spceics ulilite nonheme iron p-ortins,lhe hei'IICt)'1Mn$, for these
runaions (sec pqe 908). LcbSlen. Ctllbs. spden.
and some snails use a coppcreoouininJ proran themoc:yanin, see pace 909) for oxnen transport.
Dioxyg" Binding, Transport, ond Utilizatio"
901
Cbl
Fig. 19.8 Rclwivc scale
or (a) red blood cdls. che bit>Wricul unit of clioxygen transport ; (bl
the hemoglobin molecule. the bioclrmicul unit of dioXYaen transport; and (c) the
dioxygen-hcmc group. the in.,runic- unit
dioxyeen lr.U\Sport. The relative sizes arc given
by I he factors over the arrows. (Scannina electron microsruPh
of M. Barnhart.
Wayne: State U niversity of Medicine. HcmoeJobin molulc modified from Perutz. M.:
Ros.sman. M. G.; Odlis. A. F .; Muimcud. H.: Will . G.: North. A. C. T . Noll"r ILondon)
1960. I&J. 416. Reproduced with permission.)
or
14000
10
2Cl
JO
40
SO
60
10
I()
QO
100 110
Fig. 19.9 Dioxygcn bindins aJrvd for (II myosiObin und for hemo&Jobin at various partial
pressures of carbon dioxide: (l) 20 mm Hg: (31 40 mm He; (4) 80 mm He. N01e INII
myoglobin has a stronger .nitity
than hemosJobin and thatlhis effect is more
pronounced In the presence o( lar&e amounts of carbon dioxide. (Modified from Bk. A. V.;
Field. H . J r. ; Adair. G. S. J. Bioi. Clrm. 1924. S9.
Reproduced with permission.(
ror
902
1 9 The lnorganoc Chemistry of Bialagical Systems
curve shown in Fig. 19.9 is obtained. My()81obin is largely converted to oxymyoglobin

even at low oxygen concentrations such as occur in the
(3) The equilibrium
constant for the formation of oxyhem()81obin is somewhat more complicated. The
expression for the curve in the range of physiological importance in the tissues is:
(19.14)
The 2.8 exponent for dioxygen results from the factlhat a single hemoglobin molecule
can accept four-(Jioxygen molecules and /he binding of /he four is not indepetcdenl. It
is not the presence of four heme groups to bind four dioxygen molecules per se that is
important. If they acted independently, they would give a curve identical to that c:l
myoglobin. II is the cooperalivity of the four heme groups that produces the curves
shown in Fig. 19.9. The presence of several bound dioxygen molecules favors the
addition of more dioxygen molecules; conversely, if only one dioxygen molecule is
present. it dissociates more rendily than from a more highly oxygenated species. The
net result is that allow dioxygen concentrations hemoglobin is less oxygenated (tends
to release 0 2 ). and at high dioxygen concenlr.nions he.moglobin is oxygenated almost
to the same extent a.s if the exponent were I . This results in a sigmoid curve for
oxygenation of hemocJobin (F"c. 19.9). This effect favors oxygen t ranspon since it
helps the hemoglobin become saturated in the lungs and deoxygenated in the capillaries. (4) There is a pH dependence shown by hem08fobin. This is known as the Bohr
Hemoglobin binds one H + for every two dioxygen molecules released. This
favors the conversion c:l carbon dioxide. a metabolite of the tissues, into the hydrogen
carbonate ion (HCO) l promoling its transport back to the lungs. Likewise. the
production of carbon dioxide from ceU respiration and of lactic acid from anaerobic
rneubolism favors the release of dioxygen to lhe tissues.
Structure and
Functio n of
H e mogl obin
Hemoglobin may be considered an approximate tetrame.- of myoglobin. It has a

molecular weight of 64.500 and contains four heme groups bound to four protein
chains (Fig. 19.8b). Two of the chains, labeled beta, have 146 amino acids and are
somewhat similar to the chain in myoglobin; the other two. labeled alpha. have 141
amino ucids and are somewhat less like the myoglobin chuin. The differences between
ht:moglohin and myoglobin in their behavior tow:ords dioxygen lpanicularly 3 and 4
above I arc related to the structure and movements of the four chains . If the tetr;,meric
hemoglobin is broken down into dimers o.- monomers. these effects are lost . and the
smaller units do not exhibit cooperativity. Myoglobin docs not exhibit the sigmoid
curve nor a Bohr effect.
Upon oxygenation of hemoglobin. two of the heme groups move about 100 pm
towards each olher while two others separate by about 700 pm. Perhaps a beller way
of desaibing the movement is to say that one all half of the molecule rotates IS"
relat ive to the other half..JO These movemenes are the result of a change in the
quaternary structure of the hemoglobin and are responsible for the cooperative effects
observed. The quaternary structure exhibited by the deoxy form is called the T stale,
,., DiscovCRd by Chr!sliM llollr. falhcr d Nlc:IJ Bohr. lhc pioneer or """num mcct..nic:s.
R. E.: Gas. I. TM
und Arti'un t1{PrtllritU: H:lrJ> & Row: New York. t969;
p 5\1: Hmurlobin:
Function. l::o'OIIIIion. onJ Putholog: Bctti:>min/Cumrnirlp: Menlo
Pork. CA. 1983. Baklwin, J.; O!olhia. C. J. Mul. Bioi. lln9. 129. t7S.
JO Dickc:non.
Oioarge n Binding, Transport, and Utilization
903
and that oftheoxy form lhe R stale.Jt The dioxygenaffinity of the R form is about the
same as that of isolated a and 13
butt he dioxygen affinity of the T stale is some
12-14 kJ mol- 1 lower. This fundamental difference in the energetics of dioxygen
binding is responsible for the cooperntivity of hemoglobin. The lower affinity of the T
form is responsible for the slow start of the sigmoidal curve (lower lefl. Fig. 19.9). and
the higher affinity of the R form causes the rapid rise in the curve (upper right,
Fig. 19.9) until it almost matches that of myoglobin.
Perutzn has suggested a mechanism to accounl for the cooperntivity of the four
heme groups in hemoglobin. Basically it is founded on the idea that the interaction
between a dioxygen molecule and a heme t!fOUp can affect the position of the procein
chain attached to it. which in turn affects the other protein chains through hydrogen
bonds. etc . and evencually the teniary and quaternary struccure of the protein . It has
been dubbed the Rube Goldberg effect after the marvelous mechanisms of ropes.
pulleys. :md levers in Goldberg's cartoons.n A simplified illustration of the Perutz
mechanism is shown in Fig. 19. 10.
The key or trigger in the Perutz mechanism is the high spin Fellll atom in a
dioxygen-free heme. As we have 'een. the r-Jdius of high spin Fe! is too large to lit
within the plane of t he four porphyrin nitrogen atoms. The iron atom is thus forced to
sit above the center of the heme group tFig. 19.6; Fig. 19.llal with an Fe-NP'>'Ph>rin
distance of about ::!06 pm. Funhermore. che heme group is domed upward towards the
proximal histidine.
-...
Fig. 19.10 A schcmutt.:
l'cnat7. oncch:anism in hcmo!'fobin . The three most
imJ1<1nant f:acloN arc
Ill the environment t>fthc heme: (:!I the m11vcmcnt
(lcn.siunl O( lhc pYIIIdn chains. nn.J Ill the breaking Of hydrojlCR bonds ("SUit bridges' ').
ICuunc:sy of Professor M. l'cnuz. Rcproducc<l with permission.)
from the adjC'Ciivcs ,,.,u'* 3nd rt!IIL'tc''' thttl hoW' b,n applied to Ihe 1wo slruciUrcs.
nature. Ihe
:lt'\l.l CVCO the C:< iSitnCC of '"lci\.Si.Jn.. in One (orm Ollhc OCher
ma.llcr uf con"'idcr!'t*
""": shalllt\C r ;and R
for 1hl:
structures
wnbtMJt -arucJuraJ or
$.> l'cnnt.. M. F.
rl.umlm/19'711. !!.Y.
Br. ,11<<1. Bn/1. 197fl. J!. 195. Pl:rutl. M. F.: fermi.
G .: Lui.<i. U.: Shaanan. U.:
N. C. An. Chm. Rr.<. 19117. Zfl. JOCJ. Pcrulz. M. Mt'f:h<JniJnu u/Ccm/)c"f'flfhily dnJ A/I,JttC'nc Rc:.:ulctritHt in Prttll"itU : Cambridge
Co.1mbridce.
ll The 1C:rrn5 com.:
l(llWt:V\.'f,
Ihe
>. lluhy. J . F.. In RE.ICTS IVlJ.

uf tltr
Annunl
T<'UdtinJ: Srm
pmi11m:
K.:
A.: Wun. '' J . K.: Zklick. C .. E<ls.: UnivcrsilyofMorytan.J: Collc
Park. 197); pp S2-711.
9 04
19 The Inorganic Cheonistry of liologicol Systeons
1111
11
Qo
Fe
_jJ
ICI
"''
Dioxygen Binding, Tronapo<l, and Utilization
905
The coordination oflhe dioxygen molecule as a six th ligand causes spin pairing to
lake place on the iron atom. Since the radius of low spin Fe(ll) is about 17 pm smaller
than high spin Fe(II). il should fit in lhe porphyrin hole; we expect the smaller iron
atom to drop into the hole. As a maller or rae I, il does move about 20 pm towards the
porphyrin ring
19. 1lb) and the Fe-Np<>rphynn distance shonens lo 198 pm.
However. il stops shon of moving all 0( the way into the plane or lhe ring. Data for the
heme in myoglobin, hemoglobin. and related species are given in Table 19.1.
Table 19.1
Distances (pm) one! angiM M in various heme adclum
P,...,...:-N;..._
Compound"
WhaleMb
Mb{Oz)
HumanHb
Hb{Oz)z
Hb(Oz)4
Picket
(a) 1-Melm
0 2 adduct
(b) 2-Melm
0 2 adducJ
Dab from
"
206
204
198
222
207
215
220
200
197.9
206.8
203
l9S
209.5
199.6
2 10.7
42
2h7
(N,_J'
39
18
228
38
268
18
0::!: 5
266
210
58
40
252
217
8.6
31
hrutz. M. F .; Fcnni, G.; Luisi, 8 .; Shaan&n, 8 .; Liddii1Jion , R. C.
value or scvmol methods
h-0
Lfe-0-0.
183
liS
182
176;!: 10
153
156
164.S
130
189.8
129
Ch<m. Rt!s. 1981,10, J09-J21.
or determination. See reference in Footnote o for details .
Bond lcllgths.
4 Distance between llle iron alom and the plane or the .wtroaen atoms in pollf\yrin ring. - - Distance between the nitroscn 111om in the ptoximal hislidinc (or iridazolcs in the pickct-fcocc compounds) and the plane or the
pollflyrin rins.
MovcmtN or ahe proximal histidine (or imida zole) towards the porphyrin rins upon oxygenation.
"Picket fence" - tcJnkia(t,l,l.t-<>-pivalamidophenyl)porphinutoiran(ll) (fig. 19.4); t-Mclm

(1'{-mcth)limidazole); 2-MeJm 2-mc:tllytimidazolc.
lmcthylimidllZole
19.11 The "triagcr action" of the Pcrutz mechanism in hemoglobin. (a) Ocoxy-T accepts a dioxygen molecule, 0,. to
form oxy-T (b) wilb partial movement o( the iron atom into the ring, which is strained and unstable. Addition of more
dioxygen molecules at other sites results in a rcamngement or oxy-T to oxy-R (c) with the iron atom moving complelcly
into the rin&- (d) The configuration about the heme group wilh respect to Leu FG3 in lhe T nnd R fonns. Note that the
ftatteninc of the pollf\yrin on aoins from deoxy to oxy exerts a
on leucine FG3 and valine FGS which lie at the
switching contact between the two structures. The vcnical bars indicate the disrancc of Nhb of the proximal histidine F8
from the mcun plane of the porphyrin nitrogens and carbons. The horizontal bar gives the Fe-N,_ distance, and the
vdluc to the riaJ!t or the iron atoms gives the displacement of the iron from the plane ot the porphyrin nitrogens. N01c lbat
the porphyrin is lla1 only in oxy-R and that the proximal histidine tihs relative lo the heme normal in lbe T structures. NOic
also the water molecule allached to the distal histidine in deoxy-Hb. The differences in heme s eomctry between lbe
dcoxyhemcs in the T and R structures shown here arc dosdy similar to those found between slerically hindered 2-mcthyland unhindered 1-mcthylimidazole adducts with picket-fence porphyrin. (From Peruu. M. F.; Fermi, G. ; Luisi, 8 .; Shaanan.
8 .; Uddinaton. R. C. Ace. Cht!m. Rs. 1987, 20. 309-321 . Reproduced wilb pcrmissjon.f
906
19 The lnorvonic Chemistry olliologicol Systeows
Tile inhibition of free movement of the iron atom into the porphyrin ring
been
attributed to steric interactions between the histidine ligand (which
follow the
iron), the associated globin chain , and the heme group.l4 This apparendy
in
considerable strain on the oxyheme and associated tertiary structure of the globin
the addition of the first molecule of dioxygen, or
within the T form.
more important. it "pushes" the last dioxygen molecule off in the tissues. where it is
needed. Addition of a second dioxy11en molecule takes place with similar
and.
in effect. the hemoglobin molecule
spring-loaded. The
of the
bis(dioxygen)-Tslllte has been determined and
little movement of the iron atom
and negligible movement of the histidine. The addition of a third dioxygen molecule
results in interconversion to the R stale. This removes the tension of the intermediate
species and allows the iron atom to move freely into the center of the porphyrin ring
(F'ag. 19. 11c). The porphyrin ring
llattens . and the histidine is free to follow the
iron atom, some 50-60 pm. This change allows the fourth heme to accept a dioxygen
molecule without paying the price of the protein constrninl and accounts for the
avidity of Hb{Oz)3 for the last dioxygen molecule. The relaxation of the globin-heme
interaction in the R state versus the crowding in the oxy-T state is shown in
Fig. 19. 1ld.
Support for the view that the globin portion of the molecule produces a constraint
upon the iron atom (which would otherwise move into the heme pocket) comes from
the behavior of myoglobin and model compounds (such 35 the picket-fence compounds with 1- or 2-methylimidazole mimicking the porphyrin and histidine). which
are C3Sier to study !han the more complex hemoglobin:
(_)
' cu,
..iw.:o
2 );1db)11U\Itl;lli ll\'
In myoglobin and the sterically hindered 2-methylimidazole complex (as in hemoglobin). the iron atom does not move into the plane of the porphyrin nitrogen utoms
(remaining 9 pm displaced in the complex), although it does so in sterically unhindered
indicating !hat the iron atom does indeed shrink enough to fit were
imidazole
it not constrained. The data 011 the Fc-0 bond length fit this picture: It is longer (and
presumably weaker) in myoglobin and the 2-methylimidazole/picket-fencc adduct (as
it is in T hemoglobin) and shorter (and presumably stronger) in the unhindered
1-methylimidazole/picket-fencc adduct Cand R hemoglobin).
It wllS mentioned above that the deoxy-T a= oxy-R equilibrium was affected by
pH (Bohr effect) as well
the partial pressure of dioxygen. Other species such as a
"Gdin. B. R. ; !<.plus. M. Pmc. Nod. AcuJ. S<-1. U.S.A. 1977. 7-1. Mill.
Oio"Y9.., li..di"1f, Traftsport, Oftd U.;liaotioft
9 07
single ch loride ion and 1.3-diphosphoglycernte also inHuence the equilibrium.l' Of

perflaps the greatest interest is the fact that the T- R trunsition involves tho: addition
of about 60 molecules of water to the hemoglobin. This hydratioo of newly exposed
protein surfaces stabilhes the R form which m iQht not even be capable of existence
without this h ydration energy.J6
The above discussion has been somewhat simplified masmuch as the number of
possible interactions in a molecule as large as hemoglobin is very great. On the other
hand. even as presented in abbreviated form. it is quite complicated. Various workc:rs
have placed varying degrees of weight upon different fuctors.l7 Neverthdcss. one
should not lose sight of the: fact that the iron atom Jocs undergo a chllll8e in spin state
that causes it to move. and the net result is 11 change in the quaternary structure from T
to R. And lest we get too involved in the biomechanical .. trees .. and forget to look at
the biologicnl .. forest: recall that it is the rl'dttctd affinity of the T form that is
nature's device that makes it possible for hemoglobin to pullt tilt! Jia:mtl!tt m<xecule
offin the tlssuts unJ
it to
We can thus look at dioxygen trunspon
at several levels lgo back to
19.8 and re view).
of Llioxygen to hemoglobin . two moBefore leaving tho: subject of the
lecular (genetic) d isc:ases should be mentioned. One is siC'Idc- cr/1 u11emirt ISCAI: Upon
stressful deoxygenatioo of the blood. the hemoglobin (Hbsl polymerizes and precipitates. moulting in "Severe deformation of the red blood .:c:IJs.)MTho: genetic defect
respoosible is the replacement of hydrophilic glutamic acid at
with the hydrophobic valine. The exposure of the latter upun R - T
reduces the
solubility of hemoglobin S
to normal adult hemOfllol?in. hemoglobin A.
It W.IS mentiunell above aha! heme( Fe' ' ) wall not bind dioxygcn. Heme is always
susceptible to oxidation when in the presence of o.lioxygcn .
re:1ction results from
tho: nucleophilic lli..placement of supero:title by water. and it is acioJ catalyud:.IY
(Fc:t ll t-0-0) +
W -
(Fcllll- 0 - 0 - H) .
(Felll)-0-o-Hr + H 20 - (FecllllH =OJ .
HO=
(19.15)
(19. 16)
The globin
ghcs some protcctilln by proviuing a hydrophobic environment. but
still abolll 3% of the hemoglobin is oxidized to methemoglobin Lltily. 11te enzyme
methemoglobin
ruaunas the u'iLiir.ccl
to the + stJt.: ordinarily.
H,wcver.
in<livi!lu:tls have an inhum mctothclic ,ldcct thai prevent s ahe
J' Fur an
Ji,_,.;u""ion of the
of
,,.,,.,mntplrit liJ.:tmJx. \CC rcrUl1.. M. ,\l(r lm.lliJmS

IYYO.
"'Columbo. M. F.: lliW. 0 . C. P."""--r;ian. V. A.
IY'IZ. !So.
ttl
,,J AtlostC"rtl" Rt'l:Hiull'mt iff l'ra.,ritu :
s,.;..,,.,
uf 1"" >ut>j<cl from dilrorcnl J><nl$ o( V<cw . <oe Footnm<

1111 CoUm:.n. J . P.:
Hulpa1 . T. 1!.: Su>Jick. K. S. In Mrtu/ l mr
tt{ DixJicn: Spiro. T. G E.t.: Wiley: New
Yt>rl< . l'lM: Cllaracr I; lknini. 1.: Rann. J. K.: Elli. W. R. Jr.: F,....<n. S.: GW!;<:. G.: Gry.
H . R.: ll>crs. J. A.: J.nk."M>n, G. R.: KnrJct. J.: t irp:.nJ. S. J .:
C.: l!:o)mund. K . N.:
Saicfcl. F.. 1.: Thdl. li. C.: V.llcnlinc. J . s. lliiNIH,Jitlllic Cltrlfmtry :
s""'"''" lltkok.. :
V..tlcy. CA: in pn:S>.
"' NUiic:c l h:>c lhc Ml blooiJ
in lho ru-r rithlhun.t corner Oli
IY,II .- hon lly sit:ktal.
Etyahro.:yln 11-..1 .,.., ilickkd antlt)( llow as re:adoly I
lho
., nurmal red bloo.J
c:clb. :>ll.t they :an: mort ....a:pcibk In mll3nicol
"l'hc.<o< (ao:IO<S oJ:
(or lhe
symploms of $ictlc cell ....._._..
n For
,. Slubma. K.
cr...,.
t-. 8J. 7J.
908
19 The lnot'ganlc Chemistry of Biological Systems
lion of methernoglobin.40 In addition. any individual, but especially an infant. may

be stressed by nitrite/nitrate intoxication. in which case methemoglobin is produced
faster than it can be reduced. In either case the iron( III) impairs dioxygen transport
and causes cyanosis disproportionate to its abundance. This is because iron(lll) is
small enough to lit into the porphynn ring without binding a sixth ligand. making
methemoglobin very similar in structure to oxyhemoglobin. The presence of two or
three iron( III) atoms can lock a hemoglobin molecule into the R state so that even the
heme group(s) carrying dioxygen cannot release it readily. Recall that R hemoglobin
has about the same dioxygen affinity as myoglobin. so the cooperativity mechanism
has been defeated .2
Other Biological
Oioxygen Carriers
Hemerythrin is a nonheme, dioxygen-binding pigment utilized by four phyla of marine

invertebrates. fts chief interest to the chemist lies in certain similarities to and
differences from hemoglobin and myoglobin. Uke both of the latter, hemerythrin
contains iron( II) which binds oxygen reversibly, but when oxidized to methemerythrin
(Fe 3+) it does not bind dioxygen. There is an octameric form with a molecular weight
of about 108.000 that transports dioxygen in the blood. In the tissues are lower
molecular weight monomers. dimers, !rimers, or tetramers.l And just as hemoglobin
consists of four chains each of which is very similar to the single chain of myoglobin.
octameric hemerythrin consists of eight subunits very similar in quaternary structure
to myohemerythrin. A major difference between the hemoglobins and hemerythrins is
in the binding of dioxygen: Each dioxygen-binding site (whether monomer or octamer)
contains two iron( II) atoms, and the reaction takes place via a redox reaction to form
iron(lll) and peroxide
Oxyhemerythrin is diamagnetic, indicating spin coupling
of the odd electrons on the two iron(lll) atoms. Mossbauer data indicate that the two
iron(lll) atoms are in different environments in oxyhemerythrin. This could result
from the peroxide ion coordinating one iron atom and not the other. or from each of
the iron atoms having different ligands in its coordination spllere. The first evidence
concerning the nature of the ligands came from an X-ray study of methemerythrin .... It
indicated that the two iron atoms have approximately octahedral coordination and are
bridged by an oxygen atom (from water. hydroxo. or oxo), aspartate, and glutamate.
The remaining ligands are three histidine residues on one iron atom and two histidines
on the
This is a rather small difference, but it can be reconciled with the other
..,The classic case is of the "blue Fusa1es" or Troublesorn<: Creek. KY. tlacenll:JniS of a sinbk
cOUple. each of wltom c:uried lhe receuive sene. Mansouri. A. Jim. J . M,J. S<'i. 1985. 189. :!00.
'Thoe "blue babies" result because infan1s have feaal hemosJobin. hernoslobin F . Hb,, dilfcrs from
Hb,. (:\dull hem()Giobin) and has a higher oxysen affini1y thai
dioxysen lr:>nsfer in Him>
from lhe molher's Hb,.. HemosJobin F. which is &radually replaced durin& 1he m. year of life. is
more susceplible 10 oxidation !han aduk hemosJobin. melhemoslobin is produced more readily. and
oxysen transport is rec!uc:ed. A dilfe.r ent, curious aspect of Hbp is lh<>l il proteciS the infanl
Uemporarily) from lhe SCA problems ofhernoslobin S!
A! For a review o( rnelhemoglobinemia. see Senozan. N . M. J . Clwm. Jut. 1985,61. 181.
U should be remembered lhal what lhe chcmisl glibly caDs "hemerylhrin" is nol ncccss.vily lhe
.arne from one species 10 the nex1: The foor phyto in which hemc.ryahrin is found eomprise
lhousnn<ls of pecics. ThU$ seneraliz.ations tend 10 be difficub and
oversimplified. For
reviews ofhemerylhrin cllemislry. see Klotz. I. M.: Kuru. D. M .. Jr. AIT. Clwm. Rts . t934. /7, 16.
Wilkin. . P. C .; Wilkins, R. G. Coord. Ch<m. R<v. 191!7, 79. 19S
.. Saenkrunp. R. E.: Sleker, L. C .: Jcn10en, L. H. l'rfX'. Not/. MnJ. S<'i. U.S. ;I. 1976. 7J. 349-JSt.
"The
indicaled !hat Ihe second iron nJom also hod 31yr05ine residue anacht.-d 10 il . l.:llcr
relinemc:nl or Ihe sti'Uefure showed that il is actually penlacoonlinale, bul the nr;urro:nt remains the
$al!le.
Dion.n Binding. Transport, and Urilizatian
909
data, and so until recently the consensus has tended to favor a simple pcroxo bridge
between the two iron atoms:
Fe 11
Fe11
___._I____,_--1.1_+
Few._o-o:=--Fe111
(19.17)
where the continuous line connecting the two iron atoms is a simplified representation
of the coordination spheres and the protein chain holding the iron atoms in place.
Militating against this simple structure is the fact that the MOssbauer spectrum does
not distinguish the iron atoms in deuxyltemtrythrin. If the difference in amino acid
environment is sufficient to d istinguish the iron atoms in the MOssbuuer spectrum of
oxyhemeryth rin, why not in deoxyhernerythrin?
Further data on this mauer came from the Raman spectrum of oxyt ' 6 0 180)
hemerythrin. which shows the two oxygen atoms to be in nt"Hreqlliltrff'nt positions.""'
Of the various alternative structures that have been proposed. the Raman data are
compatible with only two:
/ ' \Fe
Fe111
111
data. as well as other spectroscupic

are compatible with structure
Ill. but the quesliun was still open until the X -roy st ructure of oxyhemerythrin was
further refined:"' The proposed structures of deoxyhemeryt hrin anJ oxyhemerythrin
are:
(1 9.18)
Note that the hydrogen atoms cannot be located at this level of resolution and so the
hydrogen bond shown is merely one sua&:estion for the possible
of the
peroxide ion.
Another oxygen<ontaining pigment is confusingly named ltf'mocyanin. which
<Xlfltlins neither the heme group nor the cyanide ion; the name simply means "blue
.,. Kwtz. D. Ill Jr.; Sllriver, D. F.: Klott. l. M. J. Am. CtwWI. Sue. t976, 98.
Ornn. Rf'V. 1977.24. 14S..I78.
c.,.,J,
n Gay. R. R.; Solomon. E. 1. / . Am. Ootm. Soc. 197&. /00, 1972.

.. Slcnkamp, R. E.; Siebr. L C.; Jonsen, L H.; McCallum. J. D.; Sandcn-Lodv. J. hoc. NotL
Acod. Sci. U. S. A. 1915,81. 71l-716.
91 0
19 The lno..,anic Che011istry of l iolotical Syst-s
blood'': Whereas hemoglobin turns bright red upon oxygenation. the chromophore
(Cut/Cull) in colorless deoxyhemocyanin turns bright blue. Hemocyanin is found in
many species in the Mollusca and
The gross molecular struct ures of Lhe
hemocyanins in the two phyla are quite different , though both bind dioxygen cooperatively. and spectroscopic evidence indicates that the dioxygen-binding centers are
similar. T he dioxygen
site appears to be a pair of copper atoms. each bound by
three histidine ligands (Fig. 19.12). The copper is in the + I oxidation state in the
deoxy form and + 2 in the oxy form.
The structure of oxyhemocyanin has recentl y been determined.SO It presents yet a
third mode of binding between oxygen-carrying metal atoms and the dioxygen
cule. The latter oxidizes each copper(!) to copper(ll) and is in tum reduced to the
The two copper(II) atoms are bridged by the peroxide ion with
peroxide ion
bonds, i.e., each oxygen atom is bonded to both copper atoms.
unusual
The p;lrallels and differences among hemoglobin. hemerythrin, and hemocyanin
illustrate the ways in which evolution has ofien solved what is basically the same
problem in different ways in different groups of animals.51
Fig. 19.12 The

bindina site in hemocyanin from
inr."uptus. The
.:npp!r atoms
indicoted by open circles, the ht..
by pcnlnguM. nd t he protein
chains by ribbons. [From Volbeda, A.: Hoi. W. G . J. J. Mul. BitJI. 1989, :!119, 249-219.
Reproduced with pcnnisaion.)
.. K:vtin, K. 0 . ; Gullnd!, Y. Prog. INJrl , Chmr. 19117, JJ. 2t9-l27. The struc:1ure ol hcmocyatun
from an arthropod, lhc spiny lobJter, has been clcl..-mincd by Volbeda, A.: Hoi. W. G. J. J. Mc>l.
Bioi. 19&9, 209, 249-279.
"'
in proof: 'The complde struclure ol oayhcmocyanin has not ycl been published. bul i1
rontuins the
coordi..alion mode sho- above IMa,nus, K. C.; Tons Thai. H. J . l nmg.
1992, 17, 20). TM w uc1ure wu pRdic1ed on Ihe bosl$ model dicopper compouN!s
(Biucltbwn, N.J .; Stranac, R. W.: Farooq , A.: Hub. M. S.: Kar1in, K. 0 . J. Am. Cl.-m. Soc. 1938.
I 10, 4263-4272. Kitajilna, N.; Fujisawa. K.; Fuji11101o, C.: Moro-olca, Y.; Hashimoto, S.: Ki"'a:>wa.
T .;Toriwni, K.; T....U, K.: N:lbmura. A . J. M<. Ch..,.., $, 1,2, 1/4, 1:!77-l2911. 'The Cu-C\1
clistGncc in oll)'t>cmocyanm is l60 pen.
or
or
" For an inl.ercaJq discuasion

pe.nllcl in funclion, slruc:IU<"C, and J)ll'.'libly
ol llanoglobin. hemerytluin. ond "-'>c:yani,., set Volbed.>, A. : Hoi. W. G. J. J. Mol. Bioi. 19119,
Dt-S46..
El-mon Tranlfr, R"pirotion, ond Pho tosynthsis
Efectron Transfer,
Respiration, and
Photosynthesis
91 1
There are several nonheme

proteins that are involved in electron trnnsfer.
They have received considerable auemion in the last few years. They contain distinct
iron-sulfur dusters composed of iron atoms. sulfhydryl groups from cysteine residues, and .. inorganic'' or .. labile .. sulfur atoms o r sulfide ions . The Jailer are readily
removed by washing with acid:
f erntdoxins and
Rubredoxins 52
(19.19)
The cysteine moieties are incorpordted within the protein chain and are thus n01 labile.
The clusters are of several types. The simplest is bacterial rubredoxin. (Cys-S)4 fe
(often abbreviated Fe 1S.,, where S stands for inorganic sulfu r). and contains only
nonlabile sulfur. It is a bacterial protein of uncenain function with a molecular weight
of about 6000. The single iron a tom is a t the cente r of a tetrahedron of four cysteine
ligands (rag. 19. 13a). The cluster in the ferredoxin molecule associated with photosynthesis in higher plants is thought to have the bridged structure Fe..S. shown in
Fig. 19. 13b. The most interesting cluster is found in cenain bacteriai ferredoxins
involved in anaerobic metabolism. It consistS of a cubane-like cluster of four iron
atoms, four labile sulfur atoms. thus Fe.s and four cysteine Hgands (Fig. 19.13cl.
Because of I he inherent chemical interest in clusters of this son . as well as their
practical sign ificance to biochemistry. there has been considerable effon expended in
making model compounds for SIUdy !Fig. 19. 14). These model compounds allow direa
experimentation on the cluster in the absence of the protein chain.sJ
Cys-S
S --Cys
Cys-s,
"-Fe/
Cys-S/
'
S-
...
Fe'....
.,....s-cys
's -Cys
Cys-s/
Cys
'Fe
(b)
(a)
Cys--s,
Fe-- S
S-Cys
'sf'Fe/
;c:-S
sct--F\ts--Cys
s--Cys
(c)
ng. 19.13 Iron-sulfur clusters in ferredoxin.: (R) Fc1S,1 in bacteriul rubredoxin: (b) Fe,S, in
photOSynthetic ferredoxin: (c)
Fc..S. in cuban..tike
n BlodwmistryufNonM-Iffl#f; Bezkun>Voiny, A &1.: Plenum: New Yortt.. t9l!O: ('hQpter 8. /ronSIf

Spiro. T. G . Ed.; Woky: New York. 19&2. The encire volumed 1\J\. /twf1l. Cltrm.
199%. .18. 1-487 is dcvoted lo iron-...,fur
Unfor1Unltcly, it was rcaival100 ..IC 10 indude
much of it in this volume lu it sllould provt 1o be very useful to the inttfCII<al rc:odcr.
Li<J. H. Y.;Schaot>en. B.: Holm. R. H . J. Arw.

S.x:. t99 t. //J. !IS29-9SJ9:
Holm. R. H .; C'ourli. S.; Wei&d . J . A. l'roR. ln<;t.
1998. J8. 1-74. and references thercin.
912
19 The lnot'ganie
of IK>Iavical
S.,st
Cl
lbl
Fig. 19.14 Model compound for a cubane.(ype Fe clwcer with a trilhiallipnd. (.,
Slereoview d (Fe.,S.(trilbid)L'J; (b) close"'lp view ofthe Fe--5 du.sler. (From SlaCk, T. D.
P.; Holm. R. H. J .Nn. Clwm. Soc. 1MI, /10, 2484-1494. Rep-ocluced with permission.]
Blue Copper
Proteins
Pemaps the three most important redoll systems in bioinorpnic chemistry are:
( I) high spin, tetrahedral Fe(II)/Fe(lll) in rubredollin,
e tc.; (2) low spin.
octahedral Fe(II)/Fe(IU) in the cytochromes; and (3) pseudo1etrahedral Cu(I)/Cu(IO
in t he blue copper
such as stellacyanin. plastocyanin, and azurin.
has
pointed out that these
centers are ideally adapted for electron exchange in that
no change in spin slate occurs. Thus there is little or no movement of the ligands-the
Franck -Condon activation barriers will be small.
The structure of plastocyanin (Fla. 19. 1$) is especially instructive in this regard.
Copper11) is d 10 and thus provides no ligand field stabilization energy in any geometry.
Because it is relatively small (74 pm), it is usually found in a tetrahedral environment.
In contrast. copper(ll) d' and is usually octahedrally coordinated with Jahn-Teller
distortion, often to the point of square planar coordination. In the case of plastocyanin, the copper is situated in a "flauenc:d tetrahedron" of essentially
symme
try, "halfway" between the t wo idealized geometries. This facilitates electron
transfer compared to a system that might be at the tetrahedral ex treme or at the square
planar
Energetically, either of the IaUer would require reorganization towards the other when electron transfer took place. Such structural changes would
inhibit the process.
The mechanism of dectron IJ'ansfer over the lona distances (of the order of
1000 pm or more) llecessit81ed by the large size of redox enzymes is one that is not
completely clear despite much current study. These transfers are critical whether one
is considering the photosynthetic center (page 917) or electron carriers such as the
c,.
S4 Gny. H . B. Ch.-m. Soc. Rn. l tN. IS, 17.
"Colmaa. P. M. ; Free.man. H. C .; Guss, J. M.; Munla. M.; Noms, V. A.; Ramshaw. J. A. Ill.;
Ve.._.,oppa. M. P. Nan,,. (Lolldon} Jm, m. lt9-324.
Electro Transfer, Respiration, aftd Photosytfte sit
913
or
Fig. 19.15. Stereo.icw or lhc copper-bindi11J site pla$1ocyunin. The four lJi;lnd residues
are His 37. Cys 84, His 87, and Met 92. Note that the JtOmctr)l about the COf)lltt is neither
tettalkclral ncr square planar. bur inttrmediale . (From Colman. P. M.: Freeman. H. C.:
Guss. J. M. : Murata. M.; Norris. V. A.: R:unshaw. J. A. M. : Venklltappa. M. P. Nu111u
(London/ 1971. 271. 3t9-324. Reproduced with permission.!
cytochromes and copper redox enzymes (above). The rote of electron transfer falls off
exponentialy with distance at long range (Chapter 13). The rote is also dependenl
upon the thermodynamic
force and. as mentioned above, facilitated when
structural changes are minimal. One may readily
why the iron and copper atoms
are not on the surface of the protein so that such long-ronge transfer would be
reason is to prevent their irreversible "COfnlption" to an
unnecessary. Surely
unusable form. And almost certainly the surrounding pmtein shield serves Ihe purpose
ofrecogaition, as yet poorly understood. that allows cytochrome c, plastocyanin. etc .
to react with the intended target species and not be ''short-circuited" by reacting
uselessly with the wrong redox agent.S<I
The determination of the structures of biologic.ally important copper-containing
retlox systems
the multiplicity of techniques that can he hrought to bear on
structural bioinorganic chemistry. Ultimately. one would like to have a highly refined,
accurate structure determined by X-ray crystallosrnphy. Yet u.vcr and over in this
chapter we shall see that this goal has not been met lor many of the most interesting
compaunds. There is a wide variely of techniques that moy be used instead to gain the
desired information. These vary in ease of application and in the quality of the results.
but by combining different techniques much can oflen be said about the active site.
Often the nature. number. and distances of atoms in the coordination sphere of a
rro:tal can be obtained by a relatively new method called utended X-ray absorption
fine structure (EXAFS). It elaborates upon the lon&known fact that X-ray abSOfPtion
spectra s how e lement-specific ..edges" that correspond to quantum jumps of core
one
,. Sccu. R. A.;Maui<.A. G. ;Gray, H. B. J . Chnn.

f9S5,61. 9)2. M)'C. S. L: EUis. W. R .. Jr.;
Crutchley, R. J.: Gray, H. B. Sckn tfi6, 1JJ, 943. Bowler, B. E.: Raphnct. A. L: Gray. H. B.
Prott. I""'1J. CMm. 1996, .18, U9-l22. l.Jana, N. ; P;ebk, G. J.; Ma&Ac. A. G.: Smith. M.; HolTman,
B. M. Proc. Noll. Acod. Sd. U. S. A. IPII'I, U . t249. Wendoloski. J. J.: Mauhcw, J. B.:
P. C.; &Jemme. F. R.
I PII'I.lJ8, 794. lllel.elldon. G. Ace. Ct.rm. IU-s. 19113.11. 160. Sec
also anidcs by dleK authors in Str11C't.
(Bnfil!/1991. 7J. 1-224. The kinc1ics ol dccrroa
lr.lnSkr ollbis sort i.s disrusscd in Chaprcr ll.
914
19 The Inorganic Chemistry of liologicol Systems
electrons to unoccupied orbitals or to the continuum. By choosing X-ray frequencies

near the X-ray edge of a panicular element, atoms of that element can be excited to
emit photoelectrons. The wave of each electron will be backscauered by the nearest
neighbors in proportion to the number and kind of the ligands and inversely propor
tiona! to the interatomic distance. lf the backscauered wave is in phase with the
original wave, reinforcement will occur. yielding a maximum in the X-ray
spectrum. Out-of-phase waves will cancel and give minima. The EXAFS spectrum
consists. then, of the X-ray absorption ploued against the e.nergy of the incident X-ray
photon. The amplitudes 3IId freq uencies of the oscillations in the absorption are
related to the number, type, and spacing of the ligands. Thus if one bombards heme
with an X-ray frequency characteristics of an iron edge, it should . in principle. be
possible to learn that there are four atoms of atomic number 7 equidistantly surrounding the iron atom.H
Some EXAFS data for copper proteins are given in Table 19.2. Confirming data
from X-ray crystallography are also listed where known. Copper is paniculariy wdl
suited for study by
paramagnetic resonanu. At the very simplest level. this
Table 19.2
The typ.. accuracy, and

extent of inlormcrtion given
by EXAFS and X-ray
crym.llogrophy .., blue
copper proteins
Compound
EXAfS (pmJ
Awrin
Cu-N
Cytochrome
oxidase
Plastocyanin
X-ray (pm)
Cu-N 189
Cu-S - 223
Cu-S .., 270
CuN
Cu-N
Cu-S
Cu-S
(His-46)
Cu-S ... 227'

CuN ... 197"
Cu-N (His-37)
Cu-S ... 211
Cu-S- (ey;84f - ,;; 213
(Met-121) ... 260

4
_ __ __ _ _Cu-N
Stellacyanio
.., 200
(His-117) .., 196

(Cys-112) 213
.., 204f
210
Cu-S (Met-92) ... 290
ThiUus. T . D.; Frank, P.; Hodpon. K. 0. Proc. Notl. Acod.

S<"l. U . S. A . 1978. 7S, 4069. Grncncwdd. C. M.; Fci1en. M.
C.; Hunain, S. S.; Van Rijn, J .; Reedijk, J .; Cantcn. G. W.

DiDChtnr. D/t>p/ryl. Acto 1986, 87J, 214.
Norris. G. e.; Anderson, 8 . F.; 841ccr, e. N. J . Am. Chtm .

Soc. 1986, JOB. 218o4.
Scon. R. A.; Cramer. S. P.; Shaw, R. W.; &inert.'H.; Gray,
H. 8. Proc. Notl. Aca4. Sci. U.S.A. 1981, 78,664.
No crysUIJosrapbie data available.
Guss, J . M.;
C. J. Mol. Bioi. 1983, /69, S21.
f Guss. J . M. ; HanoweU, P. R.; Munla. M.; Norris. V. A.;
Fn:eman, H .
1986,192,361.
7- :- - -
No EXAFS or
data amiable. Spectroscopy
indicata that lhrec lipnds an: Ill<: same u in plasloc:yanin.
"The ptexnl cli.'ICussion luu been eteally :;imptified 10 Bi.., Jhc general technique as well as ohc
infonn:uion obWned withoUI PllB in10 Jhc clc:Jails of lhc analysis. For lhc Iauer as well as Ihe
experimenlal !echnique, see Cmmer, S. P.; Hodgson, K. 0 . Prog. lnorg. Chrm. 197ll, lS. I.
Ha. R. W. Bfo-lnnnroro;c Chrtnistr:-: C:'l! Hnrwood:
1984; pp St-S7; Rehr. J . J.: de:
..,..,. J
Z3i)t.1S>'jr
. ;
.. J. r .. r .:;,_,.., Sv,. 6991 . IIJ. SIJS-St40.
Electron Transfer, Respiration, and Photosynthesis
915
method can distinguish between the presence of an odd electron (Cu2 +, d 9 , EPR
signal) and complete electron pairing ceu. d 10, no EPR signal). ugands with nuclei
having nonzero spins (such as nitrogen) will cause hyperfine splillings proportional to
the number of such atoms bonded to the copper111l atom [see page 923 with respect to
Cu(lll-substituted carboxypeptidase A). Finally. a study of the hyperfine spliuing,
some of it resulting from the copper atom s nonzero nuclear spin. can provide
geometric information (see below).
Analysis of ligand field and charge transfer absorption bands can provide information concerning the geometry of the copper site and the nature of the ligand, though
mosUy of a qualitative son; values for bond angles and bond lengths cannot be
quantified. It is often useful in this regard to attempt the
and structural
determination of model compounds and 10 try to match their properties with those of
the active sites in the melalloproteins. These elfons. combined frequenlly with theoretical calculations of the same propenies. often allow predictions to be made
concerning the nature of the aclive sites. For example, while the structures of azurin
and plastocynnin have been determined by X-ray crystallography, that of the related
blue copper protein stellacyanin has not because suitable crystals have not yet been
grown. Spectral studies have indicated that three of the four ligands (His. His. Cys)
but that the latter does not contain the
are the same in plastocyanin and
methionine ligand found in the former.$8 A combination of electron parrunagnetic
resonance and electronic spectral data with self-consistent-field calculations has indicated thai the unknown fourth ligand in stellacyanin provides a stronser field than
does methionine.59 It presumably results in a shoner Cu-X bond as well as a
flattening of the geometry more
a square planar arrangement.
The synthesis of model compounds has proved to be an interesting challenge. The
Cu2 + ion is a sulliciently strong oxidizing agent to couple two sulfhydryl groupS:
2RSH
RS-SR + :!H+
(19.20)
Thus any simple attempt to lctthiols coordinate to Cu(ll) will result in persulfides and
Cu(l).
"/
s
"cu11 L
L Cu 11 /
}
--+
RS-SR +
Cu1
(111.!1)
As shown in Eq. 19.21. it is thought that this reaction takes place through a dimeric,
bridged intermediate of coordination number .5. Copper tends to form a maximum of
five reasonably strong bonds,M so complexation with a nonlabile tetracoordinate
macrocydic ligand (N.J provides only one additional site for a sulfur ligand. The
reaction in Eq. 19.21 is inhibited. and a thiolate complex can be isolated:61
"'Gc:witth. A. A.; Cohen. S. L : Schupr. H. J.; Solomon. E. l .ltH>rtf. Clrrm. 1981.16. lll.l-1146.
"'Thomann. H. : lkmurdo. M.: llBidwin. M. J.: Lowery. M . D.: Solomon. E. I. J. Am. Cltrm. Sue.
1991. 111. 5911-591). This discus.<ion of lhe study of blue copper proteins has
been
brief. For a <:omprehcnsic diSCUliSion.
E. 1.: Baldwin. M. J.: Lowery, M.D.
Rr. 1992. 91, 521-542.
.. Sec Olapkr t2. Coppc:ttlll UN!ergoc Jahn-Tctkrdislonion when six-coonlinalc and lends IO form
four strona bonds and two weak ones tOiaplcr II) .
., John. E.: Bharadwaj. P. K.: Potenza. J. A.; Soogar, H. J.lnorg. Cltrm. 1986, 15, )065.
916
19 Tl.e lnorvanic Che mist<y of liologieal Systems
(19.22)
Finally, a pseudotetrahedral complex more dosely resembling the copper site in

blue copper proteins. including the presence of two
groups, can be achieved
by using a cysteine derivative of ethylenediamine, (HSCH1CH(C02C H,)NHCH.2
It is a softer. polydentate (though noc maa-ocyclic) ligand and wiU displace N4 :
n.
(N4Cu) +
+ N4 + 2W
(19.23)
The Cu-S bonds are about 10 pm longer than those in plastocyanin but about the
same as those in cytochrome c oxidase.6l
Photosynthesis
The photosynthetic process in green plants consists of splittins the element.s of water,
followed by reduction of carbon dioxide:
2H20 ___. [4H) + 0 2
xCO:! + i[4H)
- + (CH 20)..
(19.24)
+ i<>:t
(19.25)
where [4H] does noc imply free atoms of hydrogen but a reducing capacit y of four
equivalents. The details of the reactions involved in photosynthesis are not known.
although the broad outlines are fairly clear. In all dioxygen-producing organisms
ranging from cyanobacteria to algae to higher plants, there are two coupled photosynthetic systems. PS I and PS II. The two differ in the type of chlorophyll present and
in the accessory chemicals for processing the trapped energy of the photon. The
primary product of PS I is reduced car1xln. and the primary product of PS II is energy
in the form of two moles of ATP6' with molecular oxysen as a chemical by-product.
In addition to the chlorophyll molecules at the reaction centers d PS I and PS II.
there are several other pigments associated with the light-harvesting complex. Among
these are carotenoids, open-chain tetrapyrrole pigments, and others. These serve dual
roles of protecting the cell from light radiation and 31 the same time harvesting much of
it for photosynthesis. Some of these compounds are arranged in antenna-like rods that
gather the light energy and funnel it into the reaction centers.M
The energy of an absorbed photon in either PS I or PS II initirues a series of redox
reactions (see Fig. 19.16).65 System I produces a moderately strong reducing species
(RED1) and a moderately strong oxidizing species (0X1). System II provides a
stronger oxidiz.ing agent (0X 11) but a weaker reducins agent (RED11 ).
OXu is responsible for the production of molecular oxygen in photosynthesis. A
manganese complex, probably containing four atoms of mangllllCse. is anac:hed to a
protein molecule. It reduces OX 11 whicb is recycled for use by another excited
chlorophyll molecule in PS n. In the redox reactions the manganese shuttles between
two oxidation states with each manganese atom increasing (and subsequently decreasing) its oxidation state by one unit, but it is not known with absolute certainty what
J. A.; Shupr. H. J. J. Am. Clwn. S. 1986. /06, tlSt.
speau in metabolism
.. Dcisenho(er, J.: Michd, H.; Huber, R. Trnth Bllwm. Sri. 1985, 10. 20-248. Zuber. H.;
Brumholz. R.: Sickr, W. InN,... Compr<lwmiw Bf<wmiltf'1:
Amcsz. J . Eel.;
Elsevier. Amslerclam, 1987; pP
&>Mathis, P.; Rl.chaford. A. W. In
Contprt#tt.ulvt Bloclwmistf'1:
Ames%. J .,
Ed.: Else.X.: Amsterdam. t987; pP 63-96.
6l
Bhor.ldwl\i, P. K.:
&> /ukt105ft lril'flosphate, In imponanl
Electron Troufer, ltespirotion, oow:l Photosynehnis
917
l.U
11.:1
Ill\
:!
0..1
1
II
!_ - Cl!
.J
:i' -n.ll
:i - IUt
-a.u
- I,J
Fig. 19.16 Elec:IJ'On flow in
I and II ("Z-sc:heme'' ). Vertical axis gives mid-point redox potential with

rcdoc:in& species (lop) and oxidiz.ins species (boc.tom).
these oxidation states are.66 rn the reduced form the oxidation states may be as low as
three MnOI) and one Mn(lll). but they are more likely to be three Mn(lll) and one
Mn(IV). A suggested scheme for this redox chemistry is shown in Fig. 19. 17 in which
the active site cycles between a cubane-like and an adamantanc-like configuration.
There have been several otheT suggestions conc:eming these structures. including
[ l
Mn
Mn
o,
'.--
. I
Mn
MD
.. butterliy clusters"' and other modifications of the Mn4 conliguration.67
Chlorophyll and the

Photosynthetic
Reaction Center
The chlorophyll ring system is a porphyrin in which a double bond in one of

the pyrrole rings has been reduced. A fused cyclopentanone ring is also present
(Fig. 19. 18). Bacteriochlorophyll is similar but has a double bond in a second pyrrolo:
ring reduced, and it has a substituent acetyl group in place of a vinyl group. Chlorophyll absorbs low-energy light in the red region (- 600-700 nm). The exact frequency depe.nds on the nature of the substituents.
Based on our knowledge of the structure of chlorophyll as well as the results of
studies on the photo behavior of chlorophyll in vitro, it i.s possible to summarize some
of the features of the chlorophyll system which enhance its usefulness as a pigment in
photosynthesis.M First , there is extensive cor\iugntion of the porphyrin ring. This
lowers the energy of the eledronic transitions and shills the absorption maximum into
l'kOlohk>l. 1986, 41, ft. Babcodc, G. T . In

CompultntsiW!
Amcsz. J., Eel.; Elsevier: Amstcn!Am. t9J7; pp 125-tS&. Brudvi'G. W. J .
81-mbr. 19117. 19, 9t.
67 Sec Brudvis. G. W.: Cnbtree, R. H.l'ror.l-r.
1919,17,99-142: Que. L, Jr.; True,l\. E.
lbtJ. 1990, .18. 97-200.
.. Magicn. G . N .: lqrabam. L. L Strvcl.
126. Hindman. J. C.: Kugel. R.:
SWmickas. A.; K.otz. J. J. Proc. N..t. Mad. Sci. U . S. A. 1977, 74. s-9.
"" Dismukes, G. C.
Biochnrrisrry:
918
19 The Inorganic Che,.;stry of Biological
H'
o-r-o
Mn .,.._
o-J""-o
I o
I
_.,Mn
MooJ
Mil
/ J--oj
o-Mn........._o
1-Mn'........._ I
0
Rg. 19 .17 One proposul fur the involvement d Ma centers in !lie pllocoevolulioa of dioxyeea. (Modified from
Bruditt. G . W.; Cnabuu. R. H. Proc. Nat/. AcuJ. Sci. U. S , A. 1987. 8J.
Rq,roduced with permission.)
II ,C
ClllutuflllyU 01 1R CH 1 I
/1 IR CHO 1
II
Cll ,
cH,
Fig. 19.18 Structure of dllorophyll. The lore Rlkyl chain al the bouom b ahe phylyl srotJP.
the region of visible light. ConjuG'Ilion also helps 10 lll3ke lhe ring rigi<l. and thus less
energy is wasted in inremal lhermal degrad111ion (via molecular vibrations).
The maximum inlensily of light rtachinl( riot earth's surfuct is in the visible
region; ultr'3violet light is absorbed in the earlh s atmosphere by species such as
dioxygen and ozone (trioxygen). infrared light is :1bsorbed by carbon dioxide, water.
ecc. The absorption spectra photosynlhetic systems full nicely within that ponion of
the sun's spect rum that reaches the earth. Some of the energy o f the light not absorbed
by the chlorophyll itselfi5-capt114"ed by accessory piamell(s: !!' the octave of light
or
rrom
Eat""
919
about 3SO to 700 nm. one or more photosynthetic pigments absoros at every frequency. This is the portion of the total spectrum that is of highest intensity untl
corresponds rnther closely to the sensitivity of the human eye, another sys1em
adapted to that portion of light that reaches earth.
Thanks to careful spectroscopic and crystallographic work we have considerable
information about the reaction center in photosynthetic bacteria. and it is p robable
that the photosynthetic systems in higher plants are modifications. perhaps partial
duplications, of the bacterial system.69 The reaction center is a protein with a molecular weight of about 150.000. The heart of the reaction cemer is a pair of chlo
rophyll molecules. often referred to as the "special pair" (F"ag. 19. 19).70 The special
pair are in contact with each other through the overlap of one of the pyrrole rings in
each molecule. In addition, an acetyl group o n each molecule coordinates to the
magnesium atom of the other. The sixth coordination position on each magnesium
atom is occupied by a nitrogen atom from a histidine residue in the protein chain.
Associated with the special puir are pheophytin molec ules and quinone molecules that
accept the electron from the reaction center
19.20). Near the quinone molecuk is
a nonheme iron atom complexetl by four h lstidines and one sJutamic acid. The
electron appears to be passed t.h rough the iron a tom to the redox chain. The ""hole
(vacancy resulting in a cationic charge) in the reaction center is filled with an electron
from a cytochrome molecule (there are four cytochrome-c-type centers lying near the
special pair). The separntion of charge between the electron being passed down the Zscheme chain and the posirive charge
on the Fe(IIIH:ytochrome represems
potential energy that is utili:z.o:d in the photosyntho::sis.
Enzymes
Enzymes are the catalysts of biological systems. They not only control the rnte of
reactions but . by favoring certain gcomo:tries in the trnnsition state, can lower 1he
activation energy for the formation of one:: product ruther than another. The basic
structure of enzymes is built of proteins. Those o f into:rest to the inorganic chemist are
composed of a protein structure (called an opuenzymc) and a small
group,
which may be either a simple metal ion or a
metal ion. For example, heme
is the prosthetic group in hemoglohin . A reversibly bound group that combines with an
enzyme for a particular reaction and then
released to combine with another is
tcrrn.:d a <'ll<'tt:.ym. Both pn>sthctic groups untl co.:n1.ymes are somo:times called
cofuctors. 7 '
Structure and
Function
To illustrdte the structure ot' un c:m:yme and its relation 10 function, consider carboxypeptidase A. This puncreatic enzyme: dc:avcs the curboxyl tcrminal amino acid from a
peptide ch:ain by hydrolyzina the amide linkage :
H.O
. .. Pro-Leu-Giu-Pho: .-...,.._"
. Pro-Leu-Giu + phenylalanine
(19.26)
"'YouY:III. D. C.: Marn. D. I_ C<'IJ IN4. J9. 1: Stl. A,.. lfll7. lSIII61. 42-111.
""Dcisenhol"er. J.: Epp. 0 .: Mlki, K.; Huber. R.; Michel. H. Nu111rr (l.mul011) 1915, Jill. b18. Parson.
W. W. In N ... Conl(>rf'IU'n.<i"f' Biodl<'misrry: l'lklluSJifiMMI; Amcsz. J Ed.: Elscvjor: Atn.slcrdam. 1987: pp oll-61. Bu.lil. D. E.: G10...a. P.: Chan&. C-H: Schiffer. M.: Norri>. J. R. A,. Rt"t".
l'lt:p. Clrcom. tfll7. Jll.
" The>c: terms 3re ""' :slw:lys IJSC\I in ClKlly lhc sa""' w;,y. 5 Dioo. M.: Webb, E. C. En:.:t'"''
Jnl ed.: Ac:lclcmic: New York. 1979: Hmmn.. G. G. Etr::YtrW Coluly.<os and
Acadtmoc:
New York. 1982: Palmer. T. UfllluslattJittf( Ettzyrrws. 2nd ed.: EWs Horwood: Chiccstcr. 19BS.
920
19 Tlte Inorganic Chemistry of Biological Systems
,.,
N
e-o
O=M&
lbl
Fig. 19.19 (a) Stenooview of the special pair in the pholoreaction center. lUres I of the
chloropltyU rnoleeules are stacked upon each olher. and the magnesium alom of each
chlorophyll is coordinated by an aceuce group from the o1her molecule. (b) Close-up of the
nearer chlorOphyll molecule from part (a). The unallached acetate group is from the other
chlorophyll mole<:ule . (Modified from
J .; Epp. 0.; Miki. K.; Huber. R.; Michel.
H. J . Mol. Bioi. 1984, 1/KJ, 385-398. Reproduced with permission.)
Enzymn
921
Fig. 19.20 Stereoview or til<: photosymbetic reaction center. The photoexc.ited ele<:trOn is
tl'llMferred rrom the special pair to anoth<:r molecule or bacteriochlorophyl (801. then to a
mole<:ute or bac:teriopheophytin (BPh). then to a bound quinone (QJ. all in o period or 2SO pS.
From U.e quinone it passes throogh the nonheme iron (Fe) to an unbound quinone (not
shown) in a period of :>bout 100 J.L$. The electron is restored to the .. hole'' in the special
polir via the chain of h<:mes tHe t, etc.) in four cytochrome mole<:ules. also extremely
rapidly (- 270 ps). The special pllir here is rotated 90" with respect to Fig. 19. 19. [From
Oeisenhorer. J. ; Michel, H.; Huber. R. T"nJs Bioch.,m. Sd. 1985. !43-248. Reproduced
with permission.)
The enzyme consists of a protein chain of 307 amino acid residues plus one Zn2+ ion to
yield a molecular weight about 34,600. The molecule is roughly egg-shaped. with a
maximum dimension of approximately 5000 pm and a m inimum d imension of about
3800 pm (Fig. 19.2 la). There is a cleO o n one side that conta ins the zinc ion. the a ctive
site. The metal is coordinated approximately
to two nitrogen atoms and
an oxygen atom from three amino acids (His 69, Glu 72, His 169) in the protein chain:
or
I'ORT!ON
of
922
19 The Inorganic Chemistry of Biological Systems
(a)
(b)
f"og. 19.21 (a) Stereoview of about one quatter
carbox)'pq>(idasc A molecuk. showing

the Clnlity, the zinc atom, and the functional groups (shown with black atoms) "rgI4S
(ngllli, Tyr-248 (above). and Glu-270 (kft). (b) Stereoview of the same resion. aOer
addition of sJycyktyrosine (heavY opes> cirdes). showing the new positions of Arg-14S,
Tyr-248. and Glu 270. T he guanidinilm movement of Arg 14S is 200 pm. the hydroxyl of
Tyr-248 moves 1200 pm. and the c:asboxylnte of Glu-270 mo..s 200 pm wflen Gty-Tyr bonds
to the enzyme. (From Lipscomb, W. N. Clwm. Soc. Rn. 1972. /, 319. ReJl"oduced with
permls$ion.J
Enzymes
92:0
The fourth coordination site is free to accept a pair of electrons from a donor atom in
the substrate to be
n The enzyme is thousht to act through coordination of the
zinc atom to the carbonyl group of the amide linkage. In addition, a nearby hydrophobic pocket envelops the organic aroup of the amino acid to be cleaved
19.22)
and those amino acids with aromatic side sroups react most readily. Accompanyins
these events is a chanse in conformation of the enzyme: The arginine side chain moves
about200 pm closer to the carboxylate group of the substrate, and the phenolic group
of the tyrosine comes within hydrosen bontling distance of the imido group of the Cterminal amino acid, a shift of 1200 pm. n The hydrogen bond ins to
free carboxyl
group (by arginine) and the amide linkage (by tyrosine) not only holds the subst rate to
the enzyme but helps break the N-C bond. Nucleophilic displacement of the amide
sroup by an attac.king carboxylate sroup from a slu tamale eroup could form an
anhydride link to the remainder of the peptide chain. Hydrolysis of this anhydride
could then complete the cycle and rqene.rate the oriainal enzyme. More likely. the
glutamate acts indirectly by polarizing a water molecule (Fig. 19.22b) that attacks the
amide linkage.
This example illustr.lles the basic key-and-lock theory first proposed by Emil
Fischer in which the enzyme and substrate fit each other sterically.
there is
more to enzymatic catalysis than merely bringins
together. There is good
evidence that the enzyme also encourages the reaction by
a
on the bond
to be broken. Evidence comes from spectrOScopic studies of enzymes containing
metal ions that. unlike
show d-d tr.t.nsilions. The spectrum or the enzyme
such a metal ion provides information on the microsymmetry of the site of
the metal. For exa.mple.
can replace the zn: and the enzyme retains its
:Jctivity. The spectrum of carboxypeptidase A(Coll) is ..irregular.. and has a high
absorptivity (extinction coefficient). indicilting th:1t a regular
is not present.74 The distortion presumably aids the metal to effect the reaction . It has been
suggested that the metal in the enzyme is peculiarly puised for action and that this
lowers the energy of the tmnsition
The term enratic7S has been coined to
describe this state of the metal in nn enzyme.
The substitution of a di.ft'crent metal into an enzyme pruvidcs a very useful method
for studying the immediate environment of the meml she. In :Jdditiun to the use of
Co: for spc.:1ral studies. appropriate substitution allows the use of physical mehods
Cu! ). the Mossb-.suer eiTcct tFe:- l.
such elc:cuon pararnagne1ic resonance
proton magne1ic resonance rcluxation t.:chniques (Mn: "). or
cry,tallography
(with a heavy mctalutom to aiJ in the
eo:
n There is prob>bly a k>osety bound water mutcculc a11hls posi1ion when the o:nzymc is Ml o:ns;>&ed in
active cnblysis..
n Lil"'comb. W. N. Clwm. Soc. R<'v. 1972, I. J t9; TnraM<Jro, t974 .10. tlli; At-c. CIH!m. Rr.. t982,
15. 232.
> Conslcl!:r lhe rcbtion between
and symmetry. Chap1er II. Vollcc, R. L : Wati2ms.
R. J. P. Prac. Notl. Ar'tJJ. Sci. U. S. A. 1961. 59. 491. Ulmer, 0 . D.: Voltcc. 8. L B;.JiH<WJt<Jifi<'
Gould. R. F.. Ed.: A<!Vllnccs in O..Mry tOO: Americ:ln Ctlcmicol Society: Wasttincon. OC, t97t :
10.
"Gr. ......-. 10 stretch. Slr.lin. or bend.

,. Wili:uns. R. J. P. EN!ra>'uw tM"J. 26. 96.
-'
19 The Inorganic Chemdtry of Biological System&
lei
Fig. 19.22 Suggested mode of action or

A in ahe hydrolysis o( an amide
linkage in a polypeptide. (a) Positioning of lhe substr.ue on the enzyme. lnteracaions are
(I) coordinate covalent bond, carbonyl oxygen to zinc:; (2) hydrogen bonds, arginine to
carboxylate and tyrosine to amide; (3) van der Waals attractions. hydrophobic pocket to
aromatic rina; (4) dipde attrac:lion and
incipient bond formatiOn, carboxylate
(alutamate) oxygen to .:azbonyl group (amide linkage). Drawing is dioarammatic portrayal in
two dimensions of the three-dimensional StruCture. (b) Probable inae.vention of polarized
water molecule in the incipicnr brealtina of the amide (N-C bond) linkage. (C) Completed
reaction, removal of the products (amino acid and shortened peptide chain). Original
confiauntion or enzyme rdums after proton shift from aJuaamic acid to tyrosine. For a more
detailed diliCUSSion of the mechanism or catalysis by carboxypeptidase A. 5ee BreSlow, R.;
Wernick, D. L. Proc. Nat/. 'i cad. Sci. U. S. A. 1977, 74, 1303.
Enzp,.1
Inhibition and
Poisoning
925
Tile study of the factors that enable an apoenzyme to select the appropriate metal ion
is of imponance to the proper understanding of enzyme action. n The factors that
favor the formation of certain complexes in the laboratory should also be important in
biological systems. For example, the Irving-Williams series and the hanl-soft
acid-base principles should be helpful g uides. Thus we expect to find the really hard
metal ions [Group lA (I); Group IIA (2)) preferring ligands with oxygen donor a toms.
The somewhat softer metal atoms of the first transition series (Co to Zn) may prefer
coordination to nitrogen atoms (cf. rag. 9.5). The imponant thiol group, -SH,
should have a panicularly strong affinity for soft metal ions.
The usual structurnl principles of coordination chemistry such as the chelate
effect, the preference for five- and six-membered rings, and the stability of certain ring
conformat.ions should hold in biolosical systems. In addition, however, enzymes
present structurnl effects not observed in simpler complexes. An interesting example
is carbonic anhydrase which catalyzes the ill(ero:lllversion of Clllbon dioxide and
carbonates. Like carboxypeptidase, carbonic anhydrase has one zinc atom per molecule (with a molecular weight of - 30,000), in this case coordinated to three histidine
residues (His 94, His 96, His I 19)78 and a water molecule or hydroxide ion. 1l1e active
site (Fig. 19.23) contains other amino acids that may function through hydrogen
bonding, proton transfer, etc. The relative binding power of the zinc ion towards
halide ions is reversed in the enzyme (1- > Br- > Cl- > F- ) compared with the free
Zn2 + ions
>
> Br- > 1- ). This reversal could be intupreted as some son of
"softening" effect on the zinc by the apaenzyme were it not that the soft ligand CNis bound equally well by the free ion as by the cornplex.79 Furthermore, NO), CNo-.
(r a -
Fig. 19..23 Active site or

carbonic onhydrasc. 111 the
restina enzyme a
molecule (0 e 1
coordinatrs to the zlnc
"tom. All hydroge.n a toms
1\ove been omined ror
clarity.
77 Si&cl, H.: McCormick. 0 . B. Ac'c. Clwm.

t97G. J, 201 .
'"There are three human iso<Mymeo or cartlonic: anhycJn.c that dilrtr slitl)ltly in ...,;no acid oomposition. and so the stquo:ncina oombcrs ror the histidine$ dill'u arn0111 them.
79 It should be noced that this discussion is based on a compDrion of the equaibrium
of
enzymic zinc-cyanide complunlion versus IIQUtOUS zinc-cyanide complexation!. Cyanide has a
affinity ror the soli zinc ion under b01h oonditions (liability conotanl of iZntCNl.t'- 7.7 x
10 ');hence it shoUd not be concluded thai there is any lack of affinity fat cyanide in the au.ymc.
926
19 The ln""9anic Chemistry of Biological Systems
am.l N), none of which is known for exceptional softness, are bound with exceptional
strength. They are. however, isoelectronic and isostructural with the reactants and
products of the enzyme reaction, C02 , coj-, and HCO), respectively. The expl3nation appears to be a tailoring of the structure of the enzyme molecule to form a pocket
about 4SO pm long next to the zinc ion, perhaps containing an additiooal positive
center, to stabilize ions of appropriate size.
Although some mechanisms illustrate the carbon dioxide coordinated directly to
the zinc atom, this is highly unlikely. The infrared asymmetric stretch for carbon
dioxide is found at 2343.5 em_ , in the bound enzyme compared with 2321 em-a for the
free molecule, hardly compatible with a strong interaction of one oxygen atom and not
the Other. The visible spectrum of the Co2 + -substituted enzyme shows very small
shifts upon binding C02 , again incompatible with strong oxygen-metal interactions.
The zinc atom is thought to be considerably more acidic in carbonic anhydrase than in
carboxypeptidase A. The substitution of a third, neutral, and less basic histidine in
place of the glutamate anion cootributes to the greater acidity. In addition, the three
histidines are pulled back making the zinc more dectronegative and more acidic
towards the fourth position (see Problem 19.38). This polarize.s an attached water
molecule, perhaps to the point of loss of a hydrogen ion to form a coordinated hydroxo
group. The mechanism of the reversible hydration of cart>on dioxide to carbonic acid
(actually the hydrogen carbonate ion at physiological pHs) is thought to follow the
pathway shown in Eq. 19.27. Like all truly catalytic processes, il is a closed loop:80
(19.27)
It may operate either clockwise (as drawn) to hydrate carbon dioxide, or counterclockwise to release carbon dioxide (from the hydrogen carbonate anion) from
10 Benini. 1.; l..udlinat, C.; Scozzataw, A. Struct. Bonding (!krlinl 1'2. 44. 45-91. Linclskos. S.
Ad. lnorr. Bioch<m. 191l. 4, !IS.
Enzymes
927
solution (as in the blood in the lungs), depending upon the concentrations of the
reactants.
Ligands that can coordinate to an active center in an enzyme and prevent
coordination by the substrate will tend to inhibit the action of that enzyme.81 We have
seen that azide can occupy the pocket tailored to lilt he carbon dioxide molecule. This
prevents the latter from approaching the active site. Furthermore, the infrared evi
dence indicates that the azide ion acwnll. dlH!s bind the zinc atom: The asymmetric
stretching mode of the azide ion is strongly shifted with respect to the free ion
absorption. Thus the zinc is inhibited from acting as a Lewis acid towards water with
the formation of a coordinaled hydroxide ion. Other inhibitors also bind to the metal
atom. As little as 4 x 10- 6 M cyanide or hydrogen sulfide inhibits the enzymatic
ac.tivity by 85%.
Inhibition may also be effected by metal ions. Most prosthetic groups involve
metals of the first transition series (molybdenum seems to be the sole exception).
Coordination of the apoenzyme to a heavier metal ion may destroy the enzymatic
activity. Particularly poisonous in this regard are metal ions such as Hg!+. The Iauer
has a special affinity for sulfur (See HSAB, Olapter 9) and thus tends to form
extremely stable complexes with amino acids containing sulfur such as cysteine.
cystine. and methionine. The inhibition of an enzyme by HgH has been taken as an
indication of the presence of thiol groups but is not infallible. (For example. Hg:+
completely abolishes the activity of carboxypeptidase A in hydrolyzing amide linkages.) Nevertheless, the affinity of sulfur and mercury is responsible for many of the
poisonous effects of mercury in biological systems. Often these effects may be
reverset.l by addition of sulfur-containing compounds such as cysteine or glutathione.
Another sulfur donor. 2,3-dimcrcaptopropanol. has a strong affinity for soft metal
ions. Developed during World War I ns an antidote for the organoarsenic war l!'lS.
lewisite, it was dubbed British antilewisite IBAL). It has proved to be extremely
useful as an antidote for ars.:nic, cadmium, and mercury poisoning.
The inhibition of enzyme syst.:ms does nut necessarily cause unwanted .:!feels.
Consider the enzyme xanthine oxidase. It contains two atoms of molybdenum. four
Fe..S.. and two FAD (Havin adenine dinucleotide) moieties. and it has a molecular
weight or 275.000-300.000. There is no evidence that the two units IMo/2Fe:SiFAO)
are near each other or internet in any way. It is believetlthnt the immediate environment of each molybdenum atom consists of one oxygen and three sulfur atoms
may be prcseni):.C
(additional
168
pm)
238 pm
170
pm) ff/215 pm
(19.28)
O=Mo.-S- R
S- R
Redu.:cd
+c
Oxidized
The determination of a single oxygen atom at 168-170 pm (and therefore doubly

bonded) and three sulfur alums ut 23ll pm (single-bonded HS- and RS-1 in the
reduced form. or two at :!.47 pm (RS-l nod one at215 pm (S=) in the oxidized form.
cnn be made from the EXAFS spectrum.
Cumparc the action or carbon moooxi<lc on hcm<JGIObin.

1196.
"'Cramer, S. P.: Wahl. R.; Rujasopulan. K. V. J. Am. Ch..,. Sor. 1981, /OJ. n2t-7il7.
928
19 Tit lnorgonic
af Biological Systems
This enzyme catalyzes the oxidation of xanthine to uric acid:
I
H
Uric odd
(19.29)
The electron flow may be represented as:
Xanthine -
Mo -
2FezS1 -
FAD -
02
(19.30)
Uric acid is the chief end product of purine metabolism in primates, birds. lizards.
and snakes. An inborn metabolic error in humans results in increased levels of uric
acid and its deposition as painful crystnls in the joints . This condition (gout) may be
treated by the drug allopurinol which is nlso oxidized by xanthine oxidase to altoxanthine (dashed line in Eq. 19.29). However, alloxanthine binds so lightly to the
molybdenum that the enzyme is inactivated, the catalytic cycle broken, and uric acid
formation is inhibited. The extra stability of the alloxanthine complex may be a result
of strong N-H N hydrogen bonding by the nitrogen in the 8-position:
This structure resembles the hydrogen bonded transition state for the nucleophilic
attact of hydroxide ion (Eq. 19.29) where the hydrogen bond promotes the attack on
Enzymn
929
the carbon. With a nitrogen atom a1 the II- position there is no way for the alloxanlhine
to leave.IJ
A closely related enzyme is aldehyde oxidase. II also contains two
units with a molecular weight of about 300.000. II converts
acetaldehyde to acetic acid via electron flow:
Acetaldehyde __. Mo(VI)
---+
--+ FAD - - +
02
(19.31)
When ethanol is consumed, the initial metabolic product is the extremely poisonous acetaldehyde. which is kepi in low concentrotion by the oxidase-catalyzed
conversion to harmless acetic acid. The drug Antabuse, used for treating alcoholism,
is a sulfur-containing ligand, disulfiram:
Et2N-c-s-s,_c-NEt2
In the body, Antabuse inhibiiS acetaldehyde oxidase, presumably via the soft-soft
molybdenum-sulfur interaction.84 Any alcohol ingested will be convened to
acelaldehyde which, in the absence of a palhway to destroy it, will build up with
severely unpleasant effects, discouraging further consumption.
Vitamin 8 12 and the

8 12 Coenxymes85
In 1948 an "anti-pernicious anemia factor" was isolated, crystallized. and named

vitamin B 12 or cyanocobalamin. The molecule is buill around a corrin ring containi.-.! a
cobalt(lll) atom. The corrin ring is a modified porphyrin ring in which one of the
=CH- bridges between two oflhe pyrroletype rings is missing, contrllcting the ring.
The fifth and sixth coordination sites on the cobalt are filled by a nitrogen atom from
an imidazole ring and a cyanide ion. The
is an artifact of the isolation procedure
and is not present in the biological system. where the sixth position appe:!Ts lo hold a
loosely bound water molecule.
Vitamin B12 may be reduced by one electron ("vitamin B12r") or two electrons
("vitamin B1z..") to form the Co(ll) and Co{l) complexes. respectively.llll The latter is
strongly nucleophilic and readi ly undergo.:s alkylation via oxidative addition:"
(B12(Co1l l
+ CH,I
---+
1BdColll)- cH3 J.. 1-
(19.32)
Slicrct. E. I. Prux. lmN!I. nrm. t977, 11. 1-221. 11lc IYI!II Nuhcl
in Phyiotucy unci Medicine
W:l.' awunlccl ror "rtllionol ynthesii." i . c .. Ihe 1Ailoril18 or druas ror specific sites and actions.
Elion. G. 8 . In Vitm CtU. Dn. Bitt/. Jt89, 2J.l2t-ll0.
"'
above surmise is based on the known chcmi>lry between molybdenum and solf..--conuUnins
II has bcclll5088CS1Cd 11\al disulfin1111 inhibil.s lhc enzyme by oidizing cs.<enaiol sulfhydryl
JTOUP.' 10 Corm internal S-S bonds (sec Valbri, R. C.: Pictruszko. R.
216. 6l7).
Disulfiram is also used 10 prevent rcnalaoxicity rrom FL'tinum when c/s-<!iammincdichlcrojlCatinum
tlltlsec pose 9S8l is used to
ncol)lasms and uypanoromialis (sec Wyler, M. S.:
L.
A.; Sanden. J . E.; Grcnan. M. M. Srlt'ftct 1982. 217. 4'-4-1-'6).
lhoushiiO
be dicthyldilltioc:wbamate. a mdoboJ;te of disulflnm.
ou Odtiai, E .-I.
Principks of Bl l.,miJit)l qJ
Ekmt'ntr. Plenum: New Yor1t, 1987;
pp 217-211. Crablrcc, R. H.
Ot,:unom<tollit Clw-mlstry qf tlw- Trunsition Mrtth; Wiley: New
H)
"'l.
Yor1<, 191!8; pp J88-l9J.
""The r Sl8nds ror "rcclucxd" lUtd thu Cor "lUpCt-ftcluccd. " The Iauer
seem 10 be somclhina or
an
"""' rccals allot the predomi.- coon!inacion chcmislry
is ahal or
c.,( II(), with leu f C<l(lll. and very littk ror other oxidation sutcs.
07 See Chapcu 15 with respcc11o !he basicity or mc._.s In low oxidalion stiles and oxidalin aclcitOo
rcxlions.
930
19 The lnotgonic Chemistry olliolovicol
In biological systems the two-electron reduction may be accomplished by NADH and

fl:lvin adenine dinucleOI.i de !FAD). The met hyl donor is N' methyltetrahydrofolate
(CHrTHF). The Co(IJI) corrinoid (methylcobalamin) cnn then partake in biomethylation reactions:
cHJ-THXB,u<Co'>Xmethfonine
(19.33)
CH 3-Bt2 .
TH
homocysteine
Certain bacteria can methylate n01 only sulfur in orgDnic compounds but also various
heavy melllls such as Hg, As. n, Pb, Sn, Au. Pd. and Pt in anaerobic sludges. Thus
methylmercury cation, CH1 Hg+, may be formed from inorganic mercury compounds
resulting in environmental health problems (see page 947). A related reaction posed a
serious problem in the 19th century when Paris ueen. approximately Cu3 (As01l:! with
copper acetate present to enhance the color. was used as a pigment in wallpaper.
Under humid conditions certain molds would grow on the wallpaper and form volatile
trimeth)llarsine causing arsenic poisoning to those living in the premises.
When vitamin 8 1!> reacts with adenosine triphosphate (ATP), alkylation takes
place as in Eq. 19.33 with the formation of a direct carllOo-cobalt bond between
atltnosyl and the metal, formq 8 12 coenzyme (F"tg. 19.24). lt acts in concen with
several other enzymes to effect 1.2-shifls of the general type;
- c , - c 2-
-C 1-C 2-
(19.34)
One of the indicalors of pernicious anemill, a disease caused by inability to absorb B

through the gut wall, is an increase in excretion ofmethylmalonic acid as the body fails
to convert it to succinic acid.
f"o<?A srereoview of the molecubt struc:ture or vitamin Bo: (From LeMen. P. G.

;- . :-.,. S>r. 1968, ,U(lJ, 4.S. Rcproclucxd with permission. I
Enzrmn
931
Unlillhe proposed mechanism is examined, some of these rearrangements appear

unusual:
OH
H 3 C-C-H
--.
(19.35)
"s-R
It is believed that the ,eaclion startS with homolytic cleavage

the coba.lt-c:ll'bon
bond (at a cost of perhaps 100 kJ moJ- 1)1111 to yield a Co(ll) atom and a 5'-deoxyadenosyl radiCll. This radical then abstmcts a hydroaen atom (in Eq. 19.35 from the
methyl group). Migration of the -QO)SR group takes place, followed by return of
lhe hydrogen atom from S'-deoxyadenosine 10 the substl'llle. This regenerates the S'deoxyadenosyl radical, whidl can recombine with the Clll atom to form the
coenzyme.
A third type of reaction employing 8 1: coenzyme is the reduction of
-CH(OH)- groups to -CH1- groups, as in the reduction
ribonucleic: acid
(RNA) to deoxyribonucleic acid (DNA).
B 1:
unusual in several ways. The ability 10 form a metal-carbon bond in a
biologiCll system uppo:ars to be unique: These aroe nature's only org;tnometallic
compoumls.K9 It is the only vitamin known to contain a metal. It aAXars to be
synthesized exclusively by bacteria. It is not fourxl in higher plants. and although it is
essential for all higher animals, it must be obtained from food sources. hence its
designation as a "vitamin."
The fitness of cobalamin 10 serve its biochemical fundions has been variously
ascrib<!d to t.liflerent factors by t.lilferent uuthors.w Cen ninly. the <!Xistcnce of three
oxidation stales . Col. Coli. und Com , stublc in
(ant! hence biological) media
is necessary. This. in-itself. may eliminute the earlier tl'llnsition metals (without
accessible + I
st:ltes) arxl coppo:r (Cum is st rongly oxidizing). In addition.
we have -.:en that elKI J'' (IM - I tile- ) systems are ideal for oxidative addition/reductive eliminuaitm reactions . It has ulso beo:n suggested thna the llexibility of the conin
ring allows changes In conformation that may be beneficial. In this regard it may be
noted that the cobalt porphyrin analogues of 8 11 c:unnot be reduced to Co(l) in
aqueous solution. Hence the corrin ring was selected in place of porphyrin in ahe
evolution of the B 12 coball complexes.
""H:oli"Tn. J.: ..lt'r . Clwm. R-.. 19112. /S,
Kim. S.H.:
T.W. J. A'" CMm. S.x. tll&-1. i06.
ISJ17-1019.
yestenllly 0. awrcfllly bc:inc challct11c<l-chcre is inuc:ISII18 evidence of Olho:r

biolasialmrlal-covbon bonds. buf,I.W\Iike 8 1:. none of tile ...
c:ompoun.Js hus been isdotc<l
""lbis truosm
and chwact..Uc<l
.. Schr.lu-. G. N. Allll<"' Clrml. /Itt. EJ. &11/. 1976,/S, 417. O.:hiai. E..I. J . Cfwm. &hfc. 197l. lS.
6J I; Gmrrul Prittripks uf Biorlv!,Utry of t/u
EJ""""" Pknum: New York, 19!17; p !21.
932
19 The Inorganic Chemistry of Biological Syste ms
Metallothianeins91
We have seen that henvy metals can replace essential metals in enzymes and destroy
the enzymatic activity. In addition. by coordinating to sulfur-bearing amino acids in
the protein chain they might cause an enzyme to be "bent out of shape and lose its
activity. Protection of enzymes from toxic metals is thus requisite for their proper
function. Serving this purpose is a group of proteins that have the following characteristics: (I l The molecular weights are about 6000 with 61 to 62 amino acids. (2) Onethird (20) of these amino acids are cysteine (HSCH2CH(NH2)COOH] residues,
grouped in Cys-Cys and Cys-X-Cys groups (X :a a separating amino acid). (3)
None of the cysteines are linked by S-S bridges (cystine). (4) There are few or no
histidines or amino acids with aromatic side chains. (5) With such a high percentage of
amino acids bearing thiol groups and "dumped" along the protein chain,the thioneins
are able to bind several metal ions per molecule, preferentially the softer metals such
as Zn!+, Cu2 , Cd2+, Hgl. Ag+, etc. Metallothioneins containing Zn2+ and Cu2 +
might possibly be important in the tran.spon of these essential elements, but the
evidence is mostly negaaive. On the other hand, the binding of heavy metals such as
cadmium and mercury suggests a protective function against these toxic metals.
Indeed, increased amounts ofthtoneins are found in the liver, kidney, and spleen after
exposure to them. Furtbermore, it can be demonstrated that cell lines that fail to
produce thioneins are extremely sensitive to cadmium poisoning while overproducers" have enhanced protection. It has been suggested that the binding of
thioneins to cadmium and other heavy metals. with extremely high stability constants,
is one of protection alone; perhaps the reduced binding of copper. an essential metal
but one toxic in high concentrations, serves a "buffering function" of providing
copper for enzymes but not at levels sufficiently high to be toxic. The question of
whether the weaker binding of the less toxic zinc serves a similar function, or "just
happens," is moot .
For + 2 cations such as zinc(II) and cadmium( II) each metallothionein molecule
contains up to seven metal atoms. X-ray studies indicate that the metal atoms are in
approximately tetrahedral sites bound to the cysteine sulfur atoms. The soft mercury(ll) ion has a higher affinity for sulfur and will displace cadmium from metallothionein. At first the mercury ions occupy tetrahedral sites but as the number increases,
the geometries of the metal sites and protein change until about nine Hg(fl) atoms are
bound in a linear (S-Hg-S) fashion.92 Up to twelve + I cations such as copper(l)
and silver(!) can bind per molecule, indicating a coordination numher lower than four,
probably three (see Problem 12.34).
An intriguing problem about which we know very liulc is the mechanism of metal
identification by the body that triggers its response. as in the case of the build-up of
metallothioneins upon exposure to toxic metals. Perhaps the best understood of the
metalloregulatory proteins is MerR that protects bacteria from mercurial toxicity. It is
extremely sensitive to Hgl+, and distinguishes it from its congeners Zn2 + and Cd2+.
There is good evidence that the mercury receptor forms three-coordinate mercury(ll)
complexes (see Fig. 12.lc), making possible this specificily
91
"'"'i"'S
H:tmer. D. H . Ann. 11<'1'. Blndwm. 1986. 55. 91l. Dalpmo. D. C. :

I. M. JIJv. ln<Jrg.
6, Ill. Kojima. Y. :
H. R. Tr<nds Bioclwm. Sri. 1978. J . 90.
92 JohnSon, B. A.; Armitage. I. A. ln<Jrg. Clwm. 191!1. 26. lll9-ll44.
Bioclwm.
9J
J. G .: Nallln. M. J.; MacDonneU. F . M.; Ralston. D. M.: O'Hallor&A. T . V. PrOK. /Mrg.

Clr<m. 1990. JB. )2J-.412.
Nitrogen fixation
933
Nitrogen Fixation
An enzyme system of particular importance is that which promotes the filiation of

atmospheric d initrogen. This is of considernble interest for a variety of reasons. It is a
very imponanl step in the nitrogen cycle, providing available nitrogen for plant
nutrition. It is an intriguing process since it occurs readily in various bacteria, bluegreen algae, yeasts. and in symbiotic bacteria-legume associations under mild conditions. However. nitrogen stubbornly resists ordinary chemical allack. even under
stringent conditions.
Molecular nitrogen. N 2 , l.s so unresponsive to ordinary chemical reactions that it
has been characterized as "almost as inert as a noble gas .''94 The very large triple
bond energy (94.5 kJ mol- 1) tends to make the activation energy prohibitively large.
Thus, in spite of the fact that the overall enthalpy of formation of ammonia is
exothermic by about .SO kJ mol- 1, the common Haber process requires about 20 MPa
pressure and .500 c tempernture to proceed, even in the presence of the best Haber
catalyst. In addition to the purely pragmat ic task of furnishing the huge supply of
nitrogen compounds necessary for industrial and agriculturnl uses as c heaply as
possible, llle chemist is intrigued by the possibility of discovering processes that will
work under less drastic conditions. We know they eltist: We can warc/1 a clover plant
growing at 100 kPa and 25 c!
In Vitro N itTogen
Fixation
The discovery that d initrogen was capable ol forming stable compkxes with trnnsitiun
metals (Chapter 1:5) led to extensive investigation of the possibility of
via such
complexes. An important development WIIS the discovery that certain phosphine
complexes of molybdenum and tungsten containing dinitrogen readily yield ammonia
in acidic media:,.,
where thf
tetrahydrofurnn and dppe 1.2-bis(diphenylphosphino>ethane. Ph,PCH,Both reactions take place at room temperature and atmospheric pressure.
The reducing agent iRa Grignard reagent . This reaction sequence is important because
it models the in vivo nitrogenase systems that :1ppear to employ mulyb.Je num.
We should not conclude. however. that ambient temperature and pressure reactions are likely to repl:u:e the Haber-Bosch process. Despite the f:tct th:tl the Iauer
requires high t.:mpemture ilnd
it is efficient and well
it can
pro<luce large volumes of product in shon
periods. With rcspcct to the furmcr
processes, it is certain that the chemist will not be uble to keep pace with the lively
imagination of the journalist. As an interesting aside on the inherent
of the
scientist to match ever
the reader is directed to the following
selection of titles and headlines. T he first is t he title o( the initial research report by
Chatt's group in England and the
ilre he:ldlines of various reports of it in the
popular press:"
,. Jolly. W. L. Till!
ll/ t!J, Nun-Mttols;
Et1!tc:wno.l Oirrs. NJ. t%6: p n.
., CllaiL J.:
A. J.; R;duordl. R. L.
For a .-ery rc:ad:lble
aa:otmtolthe t:IJ1ywonc, indodilw the headlines on poac9l4 . ....,a...u. J. Pux., Ruy. f,..rtn. Grrnt
Br. t976.49,;!81.
..,. ui;h. G. J. Art. Clrtm. Hrs .
tTl-tilt. For
c:aJalytic reduction in aqueous solution sec Shilov. A. E. In PnJ{H<'fit,. in CokH'JiNJt,.,.,.
istry; Wdliam.s.. A. F.; Floriana, C.: Mcrl>aeh. A. E.. Eds.: VCH: New Yonc. 1992: pp 231-244.
a,..,.
The reduction o(
molecular nitrogen to ammonia in
a protic environment
Fuel-saving way to make fertiliser
Fuel break-through
More progress in nitrogen fixa1ion
Cheaper nitrogen by 1990
Basic life process created in UK lab
(London) (Jan. 3, 197.5)

The TIITies (Jan. 3, 1975)
The Guardian (Jan. 3, 1975)
New
(Jan. 9, 1975)
Farmer's
(Jan. 10. 1975)
The Province (British Columbia.
Jan. I.S , 1975)
With each retelling the story grew, until by the time it reached British Columbia. it
appeared that the press was utmost able in 12 days to duplicate what is recorded as a
6-day event in Genesis! The resultant disappointment when scientists are not able to
meet expectations benefits neither them nor the public (but that, too, is good copy for
the popular press!).
In Vwo Nitrogen
fiJCation
are several bacteria and blue-areen algae that can fix molecular nitrogen in vivo.
species and symbiotic species nre involved. There are the strictly
Both
anaerobic Clostridium pasreuri4num,96 facultative aerobes like Klebsiella pneumonilU!, and strict aerobes like A.lotobocter vinelandii. Even in the aerobic forms it
nppears that the nitrogen fixation takes place under essentially anaerobic conditions
the mutualistic species of
(see bdow). The most important nitrogen-fixing species
Rhizobium
in root nodules of various species of legumes (clover, alfalfa. beans,
peas, etc.).
The active enzyme in nitrogen fixation is nitrogenase. It is not a unique enzyme
but :lppCarS to differ somewhat from species to species. Nevertheless the various
enzymes are very similar. Two proteins are involved. The smaller has a molecular
weight of .57,000-73,000. It contains an Fe4S4 cluster. The larger protein is an azl32
tetramer with a molecular weight of 220,000-240,000 containing two molybdenum
atoms, about 30 iron atoms, and about 30 labile sulfide ions.97 The iron- sulfur clusters
probably act as redox centers. It is possible to isolate a soluble protein-free cofactor
containing molybdenum and iron (ca. I Mo. 7-8 Fe, and 4-6 s2 - ) . Recombination of
the cofactor with inactive nitrogenase restores the activity.
It seems likely that the active site for dinitrogen binding involves the molybdenum
atom. It has been established by EXAfSVM that the coordination sphere consists of
several sulfur atoms at distances of about 235 pm. An Mo-O double bond. so
common in complexes of Mo(IV) and Mo(VI), is not present. There are other heavy
utoms. perhaps iron, nearby (-270 pm). The ultimate source of reductive capacity is
pyruvate, and the electrons are transferred via ferredoxin (see page 91 I) to nitro-
.. Closlridium includes. in additian 10 the usc(IA nitroacn..fixina C.

lhe dana erous
anxrobic species C.
(causes tctonus, " loclj:lw"J, C. bowli,.,m (causes boculismJ. and C.
wtkhl (CIWKS "ps
97 Slicfd,
E. I. Prog. lnorg.
1911,12. 1- 223. Nelson, M. J .; Lind:>hl. P. A.; DrmtJohnson.
W. H. Adv.lnorg. Bkxhc>m. 19&2. 4, 1-40. BIA',mayet. S. J. N.; Slicrtl . E. I. J. Clkm. EJuc. 1985.
61. 94l.
adtkd in proof. n.e SINdurc of nilroaenasc tw now bcai.Jctc:rmined.. Geo<)iadis.
M. IIC.; Komiya, H.; O.nlcr.lb;uti. P.: Woo. 0 .; Komuc:. J. J.;

0 . C.
1991. 2J7, t6Sl.
Kim. J.: Rces. D. c.
1991. 2J7. 16n; "'""'"' t99l. J60.
""C.-. S. P.: Hnclisoa. K. 0 .: Gillum. W. 0 .: llloru:nson. L. E. J. Am. Cltrm. SOC". t9?1. 100.
Jl98-3407.
S. 0.; Bu1Jess B. K.; NeWton, W. E.: Moncnsen. L. e.;
K. 0 .
J. Am. CNm. Soc.
109. 1.so7-7SIS.
s.n .
Th Biochmistry of Iron
935
genase. There is some evidence, not strong, that Mo(lll) is involved. Two Mo(llll
atoms cycling through Mo(Vl) would provide the six electrons necessary for reduction
of dinitrogen. Alternatively, since the enz.yme is rich in
clusters. there
should be a ready flow of electrons, and the molybdenum may stay in the one or two
oxidation slates that most readily bind dinitrogen and its intermediate reductants. The
overall catalytic cycle may resemble that shown in Eq. 19.38.99
(19.38)
A schematic diagram for the production of fixed nitrogen compounds. including

the sources of materials and energy. and the overall reactions. is given in Fig. 19.25 .
Note the presence of leghemoglobin. This is a monomeric. oxygenbinding molecule
rather closely resembling myoglobin. It is felt that the leghcmoglobin binds any
oxygen that is present very tightly and thus protects the nitrogenase. which cannot
operate in the presence of oxygen. On the other hand. it allows a reservoir of oxygen
for respiration to supply energy to keep the fixation process going.
The Biochemistry
of lron100
It is impossible to cover adequately lhe chemistry of various elements in biological

systems in a single chapter. Before discussing the salient points of other essential and
trace elements, the biochemistry of iron will be discussed briefly. Iron is the most
119
toO
tuJd,J in p<onf: The structure of the Fe-Mo cofactor cited in Footnote 97 hns le.J those
author,; to suggest thlll the molybdenum does not dir.-clly panicipote in binoling the dinltrosen
molecule. The lllo is already six<aordiruue with three S lli01111S. two 0 ntoms from a homocitrtc
anion, and one N atom from a histidine in t he protein chllin. Therefore. in Eq. 19.38 the N: is
probably bound to an Fe-S duster in place o( Mo.
Crichton. R. R.lnorranic
qflron
Ellis Horwood: New York. 1991.
936
19 The lnorgotlic Che011istry of liologicol Syst-
&crerotd mcmbtlftc
1-----t--co,
co,
Atnitlo ectds
rrom
pllotosyntbesiJ
Oolbdlydntc rrorn photosynthais
Fig. 19.25 Schernallc dia&ram of nilf'08en:ue activity in a bacterial ce". Oubohydrate

provides reducins <:!lfllcity (fCCTedoxin). eneray (MiATP). and orpnic pn:CUTSOn rcr the
manuroaure of amino acids. [From Skinner. K. J. C/ltm. Eng. Ntws 1976, 54(41). 22-lS.
R,.produced with permission.)
abundllnt transition element and serves more biologl<:lll roles than any other metal. It
can then:fon: serve to illustrnte the possibilities available for the absorption, slor.lge,
handling. and use of an essenrial metal. Iron has re<:eived much study, and similar
results can be expected for other metals as studies of the chemistry of troce elements
in biological systems advance.
Availability of Iron
Although iron is the fourtb most abundanr element in the earth's crust, it is not always
readily available for use . Both Fe(OH) 2 and Fe{OH)J have very low sclubilities, the
latter especially so
= x 10- ";
2 x J0->9) . An extreme example is iron
deficiency in pineapples grown on rust-red soil on Oahu Island containing over 20"/o
Fe. but none of it available because it is kept in the + 3 oxidatioo state by the presence
of manganese dioxide and the ubsence of organic reducing ngenls .llll Similarly under
alkaline condilions in the soil (e.g., in geogrnphic regions where the principal rocks are
limestone and dolomite) even iron(ll) is not readily available to plants. T11e stress is
especially severe on those species such as rhododendron and azalea that naturally live
in soils of low pH. Under these circumstances gardeners and farmers often resort to
the use of "iron chelate," an "edta complex. The latter is scluble and makes iron
availllble to the plant for the manufacture of cytochromes, ferredoxins, etc. The clever
application of coordination dlemist.ry by the chemical agronomist was predated by
some hundreds of millions of years by certain higher plants. Some, such as wheat and
oats, adapted to grow on alkaline soils, have evolved the ability to exude various
polyamine-acid chelating agents through the root tips to solubiliu the iron so that it
may be absorbed.t02
oct Bta.stcd. R. C. J .
ta> Susiura- Y.; NomoiO, K.
K:;,' ,.
19?0. 41.634.
Bomli"' !Bul/11} t984. S8. 107.
The Biochamislry of Iran
937
The presence of organic chelates of iron in surface waters has llei:n related to the
"red tide."' an explosive "bloom" of algae (Gymnodium breve) that results in mass
mortality offish. It is possible to correlate the occurrence of these outbreaks with the
volume of stream flow and the concentrations of iron and humic acid .IO) At least one
of the dinoflagellates in the red tide possesses an iron-binding siderophore (see
below).'04
Within the organism a variety of complexing agents are used to transpon the iron.
In higher animals it is carried in the bloodstream by the
These ironbinding proteins are responsible for the tra.nspon of iron to the site of synthesis of
other iron-containing compounds (such as hemoglobin and the cytochromes) and its
insenion via enzymes into the porphyrin ring.IOl The iron is present in the + 3
oxidation state (Fe2 does not bind) and is coordinated to two or three tyrosyl
residues, a couple ofhistidyl residues. and pemaps a tryptophanyl residue in a protein
chain of molecular weight about 80.000.106 There are two iron-binding sites per
molecule.
Most aerobic microorganisms have analogous compounds. called siderophores,
which solubilize and transport iron( !I!). They have relatively low molecular weights
(500-1000) and. depending upon their molecular strucwre and means of chelating iron.
are classified into several groups such as the ferrichromes. ferrioxarnines. and enterobaclins. Some examples are shown in Fig. 19.26. It is obvious that these molecules are
polydentate ligands with many potential ligating atoms to form chelates. They readily
form extremely stable octahedral complexes with high spin Fe(lll). Although the
complexes are very stable. which is extremely imponant to their biological function
(see below), they are labile. which allows the iron to be transponed and transferred
within the bacteria. ruT The ferrichromes and ferrioxamines are trihydroxamic acids
which form neutral trischelates from three bidentate hydroxamate monoanions. Enterobactin contains a different chelating functional group. o-dihydroxybenzene (""catechol"). Each catechol group in enterobactin behaves as a dianion for a total charge of
-6 for the ligand. A characteristic of all of these is that. in addicion co Ihe natural
tendency of trischelates to form globular complexe s. the remainder of the siderophore
molecule consists of a symmetric. hydrophilic portion that presumably aids in transport across the cell membrane (r1g. 19.:?7).
It is inceresting that biologically functioning iron compounds such a.s hemoglobin.
cytochromes. and ferredoxins employ ironllll compounds. hut the sicJcrophores ancJ tr.ansferrins coortlinate ironclll). The reduced iron compounds within
biological systems may reflect an evolutionary history from a primitive reducing
atmosphere on eanh (see page951). whereas the siderophores are the response to the
need to deal currently with iron( Ill) in an oxidized e.uunul environment.
IGl Martin. D. F.; Martin. B. 8 . J. Chtm d11c. 1976. JJ. 614.
ocw Trick. C. G .; Ander$en. R. J.: Gillum. A.: Hillrison. P. J. Sritnct lllllJ .?/9. 306-308.
oo' Bi<KIIf'lnisJry of NonlwtrW /run; Bezlccroainy. A., Ed.; Plenum: New Yori<. 1930: O,.,pccr 4.
Kochan. I. In Bioinorrllllic cn-..:srry-11; Raymond. K . N . Ed.; ''mcrican Chemic! Society:
Washinalon. DC. 1977.
106 Uiruls. M. Struct. Bonding (BtrlinJ 1973. /7.
101
Raymond. K. N .: MOller. G.: Matunkc. 8. F. Top. C""

1984. /.?J. 49. Enlerotr...,lin is 111<:
powaful m>n(lll) chclncor known with an overall st:>bility constanl of Kr- t0'9 ll..oomi<. L.
D .; Raymond. K. N. lnDrg. Cl.nn. 1991. JO. 906).
ltl05!
938
19111 ln0'1fanic Ct..mistry of Biological Systems
Yl
o ooX
v0!( 0
OH
OH
(cJ
(b)
F"Jg. 19.26 Three types of bacterial siduopllores: (a) ckdcnichrorne; (b) de.1'errioxamine B:
(C) eaterobactin.
(;It
J;g. 19.27 1llc A-<:is isomers of metal cnterobaclillll. The met:>l Ues at the center or a
distorled oc:tahedron or the six OXYBUI atoms or the three catechol lipmds with approximalt
c, symmetry. (")The slrucwre or Iron( III) enterobactin as determined by CD Speclra. (b)

ORTEP plot or the sltuclllre of V(IV) ealerobectitl u dclcrminecl crysU!Iosraphically. Note
that allho4.wh both sLnlcWrcs are viewed dowflthe ....,oxime threefold axis and the woms
(cxcq>e Fc/V) are the same in (b) u in (a), t.h e views ..,. 180" apart. Ifrom lsicd, S. S.; Kuo,
G.; Raymond, K. N. J . Jlm.
Soc. 19'76, 98, 1763; Katpishin. T. 8.; Raymond. K. N.
Anrrw. Clomt. Int. Ed. En81. 1992, JJ, -466-468. Rq>rodUOtd with permission.]
Competition for Iron
In addition to the transport of iron. the transferrins of higher anilll3ls and the
phores or bacteria show another interesting
It c::m most readily be shown by
ovatransferrin (called cona.lbumin in the older literature) ega white. though we shall
see other examples. There is a larae nmount. up to 16%. in the protein of egg white,
although It has been impossible to lind an iron-transporting function for it there. In
fact, in some 200 species for which ovatransferrin has been stud ied. 99",4 were
completely devoid of iron binding to the protein! Ovatransferrin and other transferrins. in general. have larger stability constants towards iron( Ill) than do the various
siderophores. ll is thus quite
that they act as antibacterial agents. In the
presence of excess ovatransferrin, bllc:teria would be iron deficient since the siderophon: cannot compete successfully for the iron . Ill,, ICC
Lac:toferrin, found in mother's milk. appears to be the most potent antibacterial
transferrin and seems to play a role in the protection of breast-fed infants from c:enain
infectious diseases. II has been claimed that milk proteins remain intact in the infant's
stomach for up to 90 minutes and then pass into the small intestine unchanged. thus
retaining their iron-binding capacity. In guinea pigs , addition or hematin to the diet
abolishes the protective dl'ects of the mother's milk,109
The question of iron chelation as an antibacterial defense is receiving increasing
attention. It appears to be far more general than had previously been supposed. 11o An
interesting sidelight is that the fever that often accompanies infection enhances the
bacteriostatic action of the body's transfe.rrins.
An interesting side effect
the presence of
in egg whites is the
custom. long established before any rational explanation, of beating egg whites in
copper bowls to stabilize the foam (3!> in meringues. etc:.) The copper complex
ovatransfcrrin Stabilizes the protein
egg White against denaturation and thUS Stabilizes the foam. III
Another interesting example of this son is the competition between bacteria and
the roots c:L hisher plants. Both use chebtors to win iron from the soil. However,
higher pbnts have one more mechanism with which to compete: The Fe(llll is
re\luced and absorbed by the roots in the unc:omplexed FCI Ill form. When edta and
other chebting agents are used to correct chlorosis in plants due to iron deficiency, the
action is merely one of solubilizing the Fe( Ill) and making it physically accessible to
the
chelates are not ahsortled intact. Indeed. chel:ues that stronsly bind
Fctlll may actU;olly inhibit iron
from
root met.lium.ll!
the opposite
may occur for
whose roots are growing in
media. In lloodct.l soils
roots may be
to high levels of irontlll.
posing polcntial problems of iron toxicity. Rice plants ant.! water lilies with root in
soils transport llio.. ygen !from the air or photosynthesis. or both) to che
periphery of the roots where it oxidizes the iron(lll to ironllll). In this c:a!le the
insolubility of iron!llll hydroxide is utilized tn prmttr the plant from iron poisoning. Ill A similar problem from roo much iron occurs in pans of sub-Saharan Africa.
or
or
or
or
,., Wchh, J.: wn Bockxmr. F. M. J. Clwm. </IK. 1980. S7.
lmn: Bnkoroviny. A.. &I.: Plenum: Now Yoric. t!II!O: pp JJ6-Jl7.

no Wcinbcra. E. D. MiC'mhi.>l.
t 97l,o11, 45. Hiclcr. R. C. Struct. &lttJi,.g IB<rlU.J !Mol. 58. !5.
Iron <UHJ l,fccrit>n: Bullen, J. J.: Griffi1hs, E..
New Yor1<. 19ft7.
uo
H. J .;
S . R.; Bric8s- W, R. Natwr ILtmdll#ll t9&4, J03, 647.
11Z Olsen. R. A.: Cbr1c. R.
J. H. Anr. Sci. 1981, 611, )78-)84.
""BioNWtmMry u/
II)
Dacey, J. W . H. Sdrnc1 1980, l/0, 10t7.
940
19T11 Inorganic Chmistry of Biological Systms
The excess dielary iron is derived from a traditional fermented maU.e beverage that is
home-brewed in steel drums. II It s hould be noted in this connection that the body has
no mechanism for the excretion of iron, and except for women in the child-bearing
years, the dietary requirement for iron is extremely low.
The absorption of iron in the gut, preferentially in the + 2 oxidlltion state, was
once thought to be a result of specinl physiological mechanisms, but now is generally
agreed to be merely another aspect of the differential solubility of Fe(OH)z and
However, there is a significant differentinl in the absorption of heme versus
nonheme iron: Heme iron is absorbed 5-10 times more readily than nonheme iron . us
Since meat contains large quantities of hemoglobin, myoglobin, and cytochromes, this
difference COilld be nutritionally significant.
It is conceivable that iron could be stored in the form of a complex such as
transferrin or even hemoglobin, and in lower organisms ferrichrome apparently serves
this purpose. Such storage is wasteful. however, and higher animals have evolved a
simpler method of storing iron as [t!"itin. If iron(IIJ) nitrate is allowed to hydrolyze in
a solution made slightly basic by the hydrcJ8en cartx>nate ion (HCO)), it spontaneously forms spheres of "FeOOH" of about 7000 pm in diameter. The core of a
ferritin particle is similar and contains up to 4SOO iron atoms and apparently some
Fig. 19.28 StruciUral features of apoferritifl. The gross quaternary Sllllcture of the assembled
molecule is shown in the center and more dcWls 011 the fourfold channels (ldl), the threefold
chAnnels (upper riJ;ht) and the subufllls (loftl' ri&hl) ore also
[frOfll Harrison,
P. M.; Trcffry. A.; Lidey, T. H. J. lnortf. Biocht!m. 1986,17, 287-291 . Reproduced wilh
permission. )
Enil M. G. In Kitt-Cth-r &qclo{wdla of Oo""'icvJI Tcclonology. )Cd cd. ;

GraJSOII. M. Ed. ; Wiley: New Vorl<. tJSI ; Vel . IS. pp S7G-60l. Gordcuk, V. R.; Bac:<Ja. B. R.;
BriUenh-. G. M. An11.
N11tr. IP87,7, 41S-308.
u> Narins, D. In
of
lrM: llc:z.torovbty, A., Ed.; Plenum: New Yort<. 1980;
013p.er 3. Halbcta. L. Ann. Rn-. Nutr. ltiJ, /, lll-147.
n Rolioosoa, C. L. ;
&s..,tiol ond Troc Ef ,. nts in Biological Systoas
941
phosphiUe as well as oxo and hydroxo ligands. This core is surrounded by a prOlein
covering (called apo[errllin) that allows controlled access to the core through eight
hydrophilic channels (along threefold axes) and six hydrophobic channels (along
fourfold axes) (see Fig. 19.28). 11 is thought that the iron( Ill) enters via the hydrophilic
channels and leaves via the hydrophobic channels. but the mechanism of iron transfer
is obscure. In any event, ferritin provides high-density storage of inorganic iron
combined with ready availability.ll6
Essential and Trace

Elements in
Biological Systems
The discussion of metalloporphyrins and metalloenzymes systems has indicated the

imponance of certain meta ls in chemical reactions within living organisms. Certain
elements are essenlial in that they are absolutely necessary (perhaps in large, perhaps
in small quantities) for life processes. Other elements are nonessential since they play
no positive role in biological systems. Obviously, determining the essentiality of an
element is difficult. The term " trac;e element" although widely used is not precisely
defined. For example, molybdenum averages about 1- 2 ppm in rocks, soils, plants,
and marine animals and even lower in land animals. Yet it is an essential trace metal.
At the other extreme, iron, which averages about$% in rocks and soils and
in plants and animals. might or might not be considered a trace" mellll.
Although the role of iron in various heme derivatives and zinc in carboxypeptidase and carbonic anhydrase is clear. there are many instances in which little is
known or the function of the trace metal. For example. it has been known for some
lime thai ascidians("'sea squirts")concentrate vanadium from sea water by a factor of
a millionfold, but a satisfactory e11planation for its role in these animals remains
elusive.m There are many elements that are known to be useful but for which no
specific function has yet been proved. The list of known functions is expanding
rapidly, however .
The problem of toxicity is difficult to quantify. There are so many synergistic
effects between various componentS of biological systems that it is almost impossible
to define the limits of beneficial and detrimental concentrations. There is also endless
variation among organisms. Truly. "one man"s meat is another man's poison." The
phenomenon of an essential clement becoming tox ic at hicher than norm.1l concentra
tions is not rJre. Selenium is 3r1 essential clement in
yet one of the most
vexing problems the poisoning or livestock from eating plants that
this
element (page 9.St).
The importance of trace elements is manifold ood. unfortunately. previously
hampered by rela tively insensitive analytical methods. Good met hods for determining
concentrations of I ppm or less have been avrulable for rel01tively few elements; yet
these may be the optimum concentrations for a particul01r trace element. When the
responses of living organisms o.re more sensitive thoo the laboratory "black boxes,"
the chemist naturally develops 010 inferiority complex. Fortunately. the recent development of analytical techniques cap;lble of determining pam per billion has opened
new vistas for the study of these problems. Some of these techniques are atomic
absorption, atomic fluorescence, actiVIUion analysis, and X-ray fluorescence.
E. C. A111t.
, ,.
27,
Bitxlotm. lfl?. 56. 2lS9. Lippord. S. J. Ant""'
/111 .
Ed. &Ill. Jnl.
}C4.
m Kuain. K.; McLeod. G. C.; G;lbcrt, T. R.; BriQs. L. R. IV Sl111ct.
(Bnlinl 19113.51.
139-lf>O. Boyd. D. W.; Kllllin. K. Ad. /IID#f. Bio<Mm. l t$4, 6, )t2-l6S. Wev..-. R.; Kuslin. K.
Adv. lnof"ll. Clotm. I.!IM. JJ, 81-IIS.
942
19 The '""'11""ic Chentry of Biological Systems
Periodic Survey of
Es.sential and
Trace Elements
The biochemistry of iron has just been diS<:ussed in some detail including the biochemical species involved, bioaccumulation, tronsport, storage, and toxicity. Space
docs not permit an extensive discussion of other clements of importance. However, a
brief discussion will be presented here with a table summarizing what is currently
known.
The number of elements that are known to be biologically important comprises a
relatively small fraction of the 109 known elements. Natural abundance limits the
availability of the elements for such use. Molybdenum (Z = 42) is the heaviest metal,
and iodine (Z = .SJ) is the heaviest nonmetal of known biological importance. The
metals of importance in enzymes are principally those of the first transition series, and
the 01her elements of importance are relatively light: sodium, potassium,
calcium. carbon, nitrogen. phosphorus, oxygen, chlorine. and. of course. hydrogen.
Table 19.3 lists clements that hnve been found to be essential or poisonous,
tosether with notes on biological functions and leading references thnt may be followed by the interested reader. t il It is certain that the information in this list will be
expanded as the present techniques and theory are improved.
Biological
Importance,
Biological Fitness,
and Relative
Abundance
There are at least two ways. maybe more. of looking at the fitness of particular
elements to serve particular biological functions. The more " chemical" approach is to
suggest that iron functions well in cytochrornes and fcrredoxins because the
Fe-'
.. couple has a reduction potential in the appropriate range for lift processes
and. conversely, that mercury is poisonous because it binds irreversibly with en. zymes, destroying their activity. Basically. a given clement cannot function in a
biological role unless it has specific properties. Yet chemical properties are fixed,
biological systems are not, and there is the "biological" perspective of deciding how
those biological systems adapted to the working materials available to them: the
"fitness of the organism" to exploit fixed chemical starting materials. From this point
of view. one is immediately attracted to the question: "What are the starting materials?" It is rhcn useful to attempt to correlate biological activity with the crustal
abundance of a given element. ltv If we look at some typical essential transition
elements. we find in addition to Fe, Co. Zn, Cu. and Mo mentioned previously. V, Cr.
Mn. nnd Ni. Representative essential metals are N11. K, Mg. and Ca. and essential
nonmetals are C. N. 0 , P. S. and Cl (see page 9Sl). All of these clements except Mo
arc r.:tmivcly abundant in the
crust (Table 19.4).1211 When we look for abundant
clemr.nts that are not essential elements, we find only three-A!. Ti. and Zr-all of
which form extremely insoluble oxides at biologically reasonable pH values. No
common element is toxic at levels normally encountered, though almost anything can
be harmful at too high levels (cf. toxicity of the sodium chloride in sea water to
freshwater plants and animals). When we consider the clements that are currently
causing problems in the environment, we find that they are all extremely rare in their
""1Wo books
bem wrillcn devoted to tllis &na111

Ochiai. E.-I.
Princ/pll's of
Bi.xl..,mutry qf tlw
Plenum: New Yorlc. 1917. Bowen. H. J. M. EJ!w,onlfiC'IIWJ Chm,,.ts; Acadcmie: New Yorlc. 1979.
119 HIJhccy. J. E. In REACTS 1971, p, rnfiltr of tlw R,tli<>ffDl
Cl,..,lstry T<'odrinsl Symposwm; Eaolf, K.; Rodcz. M. A.; Won, A. J . K. ; 2ldick. C. Edt.; Univcnily or MAryland:
1m: w n-11.
' "' l!c:awie almosa ad or the earth' s cruJI is silicoot d ioxide or silicalcs, aillc011 ....ct OXYBCJI make up
ovtt 9S'/. cl the crust and ..-le. Only about two doun clcmeftiS occw with rreqomcy or one
aiOm per :o.cro alcr.>S or oilicoo; thnc
...bundanl" or "rtblivcly abl.o>clara...
lstry of
EJ..
EJ'"''"";
Essential aftd Trace El-ftts in Biolo.gical Systems
943
Tobie 19.3
Func!Min anclloJrlcily of 1M elemenra in !Hological systems
Atomic
_number
s..,.nt
Biological fvftdions
Co""'""'ls
Hydrogen
Molecular hydrogen metalxr

lized by some bacteria.
Constituent of woter and all

organic molecules.
is
toxic to mammals.
Bacterial hydrogenases are
nickel-c:onlaining en-
Helium
None known.
Lithium
None known.
Slightly toxic .
Beryllium
None known.
Very toxic.
Used to replace nitrot:en as an

Oz diluent in breathing mixtures to prevent the
"bends" in high-pressure
worll.
Used pharmacclogicaBy to
treal manic-depressive pa
tients.t
Pollution occurs from industrial smokes. There are
some fears concerning poisoning from camfng
lantern mantles.
Boron
Moderately toxic to plants;

slighUy toxic to mammals.
Carbon
Unknown, but essential ror

green algae and higher
plants; probably essential
ultratrace dement in animals.'
Synthesis of all organic molerules and of biogenetic
carbonates.
Nitrogen
Oxygen
zymes.b
Carbon monoxide is slightly

toxic to plants and very
toxic to mammals: CN'" Is
very toxic to all organisms.
Synthesis ()(prote ins, nucleic Ammonia is toxic at high conacids, etc. SlePli in the nicent ration:<.
trogen cycle (Oil!llnic NNHJ-NO! -NO)N2 -organic N)areimportant activities of certain
microorganisms.
Structural atom of water and
fnduces Convulsions aJ. high
most o.-ganic molecules in
Po-.; very toxic as ozone.
biological systems; required
suPt:roxide, peroxide, and
hydroxyl radicals!
, for
by most or-
'I
\ gamsms. ot
,.,.
"'"' ,
i,., .;. ....;_J .., , .., 1tt''
. ' . .
,. .
.....
_
)'1,'"'
.. o,.
. . . . . r J... :
1W
1-,
, J-. . \' i"
.. .,J..
"Y
Moderlllely toxic, may cause - Pollution by fluoride present

mouled teeth.
in superphosphate fenilizers. Ca. I ppm in water
,t.t... provides carioscatic action;'
, ,
, '}
in the treatment
f
' ofosteoporosis.
....
U> <li '
Auorine - Probably essential elerneRt;h

.
. usedasCaF2 bysomemol
lusks.
Carbon dioxide and CO are

global pOllutants from buming fossil fUels; CN'" is a
local pollutant of rivers near
mines.
leaching of "itrogenous renilizers from ajlriculluralland
:sntl nitrOgeRous materials in
sewage cause serious water
pollution. Nitrogen oxides
are widespread source o(
acid raio!
J.
...'.,:
-':ot
JtlJi
..
-::-:-
944
19 The lnganic O.etnistry of Biological SJ'IIOrm
Toblo 19.3 (Continued}

Atomic
num!Nr Elemetlt
Toxicity
Biological fuotcliom
None known.
II
Neon
Sodium
12
Magne sium
Essential to all organisms.

Present in aU cltlorophylls.
Has other e lectrochemicai - and enzyme-activating
functions. U .S. population
may be marginaUy deficient.!
May activate succinic deModerately toxic to most
hydrogenase and liplants; slightly toxic to
aminolevulinate demammals. Suggested as inhydrase! The Iauer is
. volved in the etiology of
involved in porphyrin synAlzheimer's disease and
thesis.'
other neurologic diseases.'"
10
Tolerance of and/or dependence upon sodium chkxide

can be an important consideration in the survival of
plants and aquatic animals.
This depends upon osmotic
regulation rathct' than sodium specificity.
May cause deficiencies of
other elements(e.g . Fe) by
the effect of the alkalinity of
dolomite.
Re latively han:nless except in

excessive amounts {lethal
doSe ca. 3 g kg- 1). Associa ted with some forms of
hypenensioo.
Important in nerve funcaioning in animals. Major cation

of extracellular fluid in animals.
13
Aluminum
Rdalively inaccessible except

in acidic media as a result of
insolubility of
Soils and waters hiah io
AIJ+ and low in
and
Ca2 implicated in neurologic diseases."
Not chemically toxic, but
LongICrnl eXPQSUre tO finely
Essential element for growth
Silicon
14
and skeletal development in --- large amounts offmely didivided asbestos from conchicks and rats:" probably . vided silicates or silica are
struction work poses a
- - - .. - - - - - essential in higher plants. - --il'\iul'iows to the mammalian - - health problem. Some evi-
dence for a negative
Used io the form of silicoa
lung.
dioxide for structural pUrcorrelation between silicon
poses in diatoms. some
content of drinking water
protozoa, some sponges.
and hean disease."
limpets. and one family of
plants.''
Phosphorus lmpottant constituent of
ll)organic phosphates are rela- Leached (rom fertilizers apIS
DNA. RNA. bones, teeth,
tively harmless; P4 and PH3
plied to agricultural land;
some shells, membr.ute ; . are very toxic in mammals
present in detergents and
phospholipids, ADP and :_.. ,, "'and fish. Pltosphaleescers
othe r sewage souroes.
ATP, and metabolic inter- ; .<are used as insecticides
16
Sulfur : .. Essential element in most pro- :;: Elemental sulfur is highly . Sulfur dioxide is a serious at' ' teins; imporunt in tertiary . ::__-,._toxic to most bacteria and
mospheric pollutant
. ': ' " ' " . structure (through
relatively barmJess to .. especially serious when it ;
.. _
. -:. ..
s-s
.. :
-:- 'links)ofJ>t:Oleins;irwoived
,.fUah.ly toxic to mammals;
. in vitamins, fat metabotism, :

. .
i"::. ,,
:-_:
. ,
> .J
..
,.. . .." . -
, and detoxific:ation pro- , .-, . ,S02 is highly toxic.

oesses.'..Hz504 indigestive ..:: .
;...,,
.. .
2"'1
.. ,.. fi:!O tn photosyntheSIS
of :
..
<or
;!
.-..
) -se.ttles inundisturbed ; ...

pockelli; oxidized to
HzS04 ; widespread cause .
ofacidrain!Sulfldeminer-
:.; . ...........:
.. .
t , :
-
; .
....
.,
Essential and Trace Elements in Biological Systems
945
Table 19.3 (ConlinU<}

AI anNe:
number
a-nt
Biolaglcollunc!ians
Comments
. Essential for higher plants and

mammals. NaCI electrolyte;
HO in digestive juices; impaired growth in infants has
been linked to chloride deficiency .
Argon
None known.
Essential to all organisms with
PotaSsium
the possible exception of
blue-green algae; major catioo in intracellular fluid in
animals; essenriaJ for transmission of nen-e impulse
and cardiac function.
Essential for all oc-ganisms;
Calcium
used in cell walls. booes,
and some shells as structural component; important
electrochemically and involved in blood clocting.
Scandium
None known.
Titanium
None known, but it tends to
be accumulated in siliceous
tiSsues.
Essentialtoascidians (..sea
Vanadium
squirts"'), which concen. trate in a millionfold from
sea water. Essen!ialto
chicks and rats. Deficiencies cause reduced growth.
impaired reproduction Md
survival of young. impaired
tooth :uld bone metabolism
and
de.elapment.
May be a factor in
manic-depressive illness.'
Chromium Essential: involved in glucose
metabolism and diabeteS;
potentiates effect of insulin." Presence in glucose
tolerance factor from
brewer's yeast que&ioned.'
Chlorine
17
18
19
20
21
22
23
24
Manganese
"
Relatively harmless as Cl- .

Highly toxic in oxidizi!ll
forms: Cl1 cro-. CIO;:
Extremely toxic 10 mammals

when injected intravenously; emesis prevents
oral toxicity:
Pollution problem possible

from leaching of fertilizers
from agricultural land.
Relatively harmless.
Mny awse ddicienc:ies or

other elements (e.g .. Fe> by
effect of nlkalinity of lime5tone.
Scaroely toxic.
Relatively hnrmkss.
HiJl)lly toxic to mammals if injected intravenously.
Highly toxic as CrtVI); carcinogenic; moderately toxic

as Crtlll).
Essential to all organisms; ac- Moderately IC?xic.

tivatcs numerous enzymes;
deficiencies in soils lead to
1
infertility in mammals. bone
: _ _ _ ' .:.. malformation in growios
,,
. t:...::
J.
.!-
Chicks. "';
-..: t.
Relatively unavailable because of insolubility of

TiO .
Possibk pollutant from industrial smokes-may cause
lung disease .
Potential pollutant since

amount used industrially is
large compared with narmal
biological levels; normally
relatively unavailable be
cause of low solubility.
Cr(V!) used in comfon
cooling towers. environmental h=d.
946
1 9 The Inorganic O.emistry of liologicol Syste"'s
Tobie 19.3 {C<>nfinu.J/

Atomic
"'"""be.
Eletwenl
26
Iron
27
Cobalt
28
Nickel
29
Copper
)0
Zinc
lltologicol functions
ToUcity"
c:o....-.rs
Essmlialto all or-p.nisms. See Normally only sli,chttoxidty, A very a.bundant dement (S"/.
ofcarth"s crust): may not be
but excessive intake can
text.
available at high pHs.
cau.sc siderosis and damaac
to organs throuth excessive
iron Slor.lic (hcmochromatosis).'
Essential for muny organisms V cry to><ic to planls and mod- Extensive areas are known
where low sool cobah aferatcly so when uuccled
iocluding m:unmals; acli!"eelS the health of grazing
vales a number of enzymes;
intr.li!Cnously In mammals.
animals.
vitamin 12
Vcry to><ic: to most pbnts.
Loc:a1 induslrial pollutant of
Esscmialtrace element.
Olic:ks and rals raised on
so to m:unmals;
air and water.
deficient diet show
carcinosenicliver function and marstabilizes coiled
nllosomes. Active metal in
several hydrogcnoses and
plant urea.ses.
V cry tollic: to most pl;>nta;
Pollution from industrial
Esscnlinlto all organisms;
smoke and pcmibly from
hil)lly toxic to in..ertc
constituenl of redox enagricultural use. Walsoo"s
zymes :mel hemocyanin."
brales. moderately so to
recessive.
mammals.
resuks in to><ic: increase in
copper storage..
Essential to all organisms;
Moderately to slichtl)' toxic;
Pollution from induslrial
smoke may cnuse lung disU$Cd in > 70 enzymes; staorally causes vomiting and
diantlea.1
eue: use ol z.ioc promotes
bilizcs coiled nbosomcs.
cadmium pollution. Certain
Plays a role in sexual matuareas (e.g., Iran and Egypc)
ration and reproduction.
are zinc deficient.o
U.S. population marginally
dcficicnr.
Mnst of tht lrtuitr tlrmtnts art comparotivdy Ullimporranl blologicaUy. Some oftht uuptions
Serious polludon problems in
Arsenic
Essenti31 ulrr..trace element in Moderately
to pla..ts.
33
some ascas: sources inelude
highly
to mammals.
red algae, chick, rat, pia,
mining. burning coal, imgoat. and probably bumans.
pure sulfuric add,
De.licicncy results in depressed growtb and
insecticides. and her
bicides.
increased mortality.
Livestock GTOWO OD soils high
Moderately-toxic to plants.
Essential to mammals IIIJd
Selenium
34
in selenium asc poisooc:d by
biahiy toxic to mammals.
some higher plants. Compo.
eating.Asll'ogcllw ("loconent of glutathione
weed'"), which conccn- .
pcroxid:Lsc, prOtects .,ain.st
tratcs it; sheep grown on
rree-radical oxidant
land
in selenium
stressors; protects q;ainst
develop "white muscle disheavy (""soft") metal
ease. Deliciency of
'
selenium iovolvcd in Keyshan disease in China."
Function unknown, but bmd
Bromine
May be cssentiai inred Blpe
except in oxidizing
and mamrn31s."-
in the molluscan piamCnt.
fonns. e., ., Br:z-
Essenrial ond Troca El..,enh in. Biological Systems
947
Table 19.3 {Conlinu.J}

Alomic
number El-nt
BiologKDI Mc:tions
37
Rubidium
None known.
42
Molybdenum
Essential to all organisms with

the possible exception of
green algae; used in enzymes conneceed with
nitrogen fixation and nitrate
reduction.
48
Cadmium
Weak evidence for ultratrace

essentiality in ratS.
50
Tin
.SJ
Iodine
Toxicity
Comments
Suppresses depressive phase

of manic-<lepressive ill-
ness.('....
Moderately toxic and antagonistic to coppermolybdewm eKcesses in

pasturage can cause copper
deficiency.' Excessive exposure in parts of U .S.S .R.
&sociated wilh a gout-like
syndrome.
Moderaldy toxic to all organisms; a cwnulruive poison in
mammals. causing renal
failure; possibly linked with
hypertension in man.
74
Tungsten
Orpnotin compounds used as

bacteriostats and fungistats;
itS use in anti-foulant boat
paints now discouraged because of danger to estuarine
and marine life.
Essential in many organisms; Sc:lrcely toxic as the iodide;
thyroxine imponant in melow iodide availability in
tabolism and growth
certain areas increases the
regulation, amphibian metaincidence of goiter, largety
morphosis.
eliminated by the use of
iodized salt. Elemental
iodine is toxic: like
and
BrRare.
Molybdenum antqonist.
78
Platinum
None known.
Pollution from industrial

smoke may be linked with
lung disease.
Has caused serious disease

("itai itai") in Japan from
pollution. Mlly also !X)$e
pollution problem associaled with industrial U$e of
zinc, e.s. galvanization.
Weak evidence for ultr.urace

essentiality in rats.
Cooccntraled up to 2.5 ppt by

some n>;lrine algae.
a,
79
Gold
None known.
80
MeraJry
None known.
Moderaldy toxic to mammals

by intravenous iqjection.
Found in enzymes in thermophilic (thermal vent)

bacteria.'
platinum( II) used as an anticancer drug!

Some use in the treatment of
Scarcely toxic.
arthritis.'..: Concentrated up
to IO%ofdryweightbycercain algae.Very toxic to fungi and green Serious pollution problems
plants, and to mammals if in
from use of Oll!atl011le1'curials RS fungicides and
soluble form: a cumulative
from industrial uses of merpoisoo in mammals.
,.
cury.
..... _
...... '""' /U>MI-J
AtOMM:
-bet
82
a.Lead
Very tox.ic to most plants;

cumulative poison in mammals. Inhibits&
aminolevulinate dehydrase
- - and thustiniosJobin syO:. thesis in mammals (see AI).
One of the symptoms of
lead poisoning is aoemia.
Toxic to central nenous
system_
May be conCentrated in oraanisms and tox.ic as a result of
radioactivity.
uv is reduced to UIV by iron.. . reducing bacteria. May be
important in the bioaeochemicaldepositcfU ...
None known.
None known.
88- 103 Radium
and
Actinides
None known.
92
Uranium
...... - '""":'"
:::--:: :-"1
'. : . -!
Woridwide pollulallt of the at-'
mosphere. concentrated in :
, urban areu from the com- j
. bustioo of
:;
Jcichl PoLJutarit : 1
. from mines; some poisoai11g
from lead-based paint pig- '
ments.
.;
Potential poUulaDIS from use I.

of Dlldenr fuel as energy ,
, source.
.
'Iro!H'c:duciog bacteria miaht 1
of use in decnntaminal- ;
ing (precipitating) unoium-
. polluted water...
:-
Toxic dTeciSol\enan: callibilc<IMy alconc:entrations above lboscoccurrina nannllyin 1henviroMI<nt. Sec p9S1.
Cnblru. R. H. Tit' 0r61Jn0-tG!Iic: Clumi.Jtr:to/tlo' TrDIUillo11 Mf'ttlis; Wiley: New Yortc, t988; pp
F'oeve. R. R.: Jamison. K. R.: Goo<Wck. P. J. In Metollorss in Nauolov Gltd l'tyclo/4ky; Gabay. S.; Hams. J .: Ho. B. T., Eds.; ..
A.bn R. Uss: New York. am: pp 107-12n.
:'
.. G<W. K. Scif'IICf' 1973. 181. 842.
Nielsen. F. H. IWI. Rw. Nutr. ln4 .f. 21.
j
1Moltnen.V. A.Sci..Nnf'r. l,._259(2),l0.
- - - - - - ---- - -,
1
FridolllCII. l Am. Sd. U?S. 6J. }4. Biolor/col Gltd ClinlcD1
of$11fHro.ridt' Gltd 5..puoziU Dimwttur. s.ooister, W. H.;
&nniua-. J. V. Ed.s.: Etsnier-North Holbod: New Yott. 1910.
!
Schw:lltz. K. F...t. Proc:., FC'd.Am. Soc. zp. BID/. 1974,JJ,I741.
- ... "'
:." . ,;
I Schnrt\$C:hu.b.R..G.: &nncs.D. . Amt. Rw. Nutr. 1911.1.421.
I
IJJ.l56.
. - - - - _ _ - - - 8ower.. H. J. M. &vir""""'rrlol CIN'mistryoftlu
Aadanic: New Yortc. 19'19. .
- - .
' !Wpu. H. A. RM<w of,.,liologkGl Chlmistry; Lanse: Los Aleoo, CA, t971.
,
- Eichorn. G. L; Bua-.J. J.:Clatk. P.; voa Halul. H.P.:Rao.G.;
0. R.:
tHfonic Clr.,.istry in Blo/oo DNI
MartcU. A. E.. Ed.; ACS Symposium Series 140; Alneric:an Ch&lnical Socidy:
Washlnaton. DC, 1980: Chapccr4. Wurtman. R.J.
62..MacDoaald, T . L;
W. G.;Mattin. R. B.
Sci4!nc' 1987. 2.16, 183.
Cacijusek. 0 . C. N. nrl. J. M ..d. l.! IIS.J/2. 7t4.

lllenz. W. Scknu 1981.1/J. 032.
1> Volcani. 8. E. Ill SiJ/con Gild Sllious
in Bio/owicGl
Simpsoo. T. L: Volcani. B. E.; Eds.: Sl)rillaer-Vcrla&:
Betlin. t981 .
.
.SU.ed. ; Olson, R. .; Vroquin. H. P .; Chichester.

Oetby, . .': -;
Nielsell, F. H.; Matt. W. In Pm,.,,
W. J.; Kolbye, A. C..
R. M..
Nutrilion Foundation:
DC, 19.8o4;Cbapler4l. : - '-! ., . ., .;;
d.
, Naylor, G. J.lnMttalloMmNeurolonDnd PJ)'d.luuy;Gu..r,s.;Hatri.s,J.;Ho,B. T.,Edt.;AiaAR. Uss:New York.t9lU; ; r
pp91- 10l.
: : i :-...- ; .. :.:
"'i
;
P. 0 .; Btad<....a. L
.
(!--'+;
Rolhn.soll. C. L; Enia. M. G. IJ>
lrd ed.; Grayson. M .. Ed.; Wilt:y: NewYorlc. .l
l9tll; Vot IS.ppS7o-60J.
.
_._ :.
i.. : :. -. '.;: 1
: ::
: :
CopJHr 1tr
on.d
Howetl.. I. M.; Gawthoroe,1. M., Eds.; CRC: lloc:aRalon. FL, I 987. Uoder,
CopJHr;Picnwn:NewYork. l"t . : .
? o!-;'.} . ".t: t.
.:. ..
l<and<r,O.
R..v.Nutr. l'1!11, 7,ZZ1.0dum,T.D.Sinld.Borrdbti(B!rlft'J IJ&l,.U,I-.t
..
w F'ocve..R.R.; JanuSOO\,K.R.Mod.Probl.l'lr""""C<lPQ'Cioi<W1 1981./8,14S. ;.-;.\:
.1 -;
'
; ''
.. C.QtJe. G. N.;P!Wice. R.
Adams.
M.
W:
....,. clt...... am ..J&.l41-J96.
:
':i. 1.
,. Pfoli,_, Gold. tutd
Almtr.Jjppard. S. I .. Ed.;ACS
Scries209;AID<rieaaChemic:al ,J&
C.O.;
-: -:-: r
:-. -:.:t;r;.
.r..
'1J.
'f
Sociely:.WISN..;.o.., DC. rmr-:::J

Corey, E.J.;Mcflrohln..M. M.; Khan.A. U.ScVnc..U17.2J6.68.
- Watkins, J .
Elder,R.C.;Grecne
. ,
_...
948
w.:u:
_lh_Pbillips,
..!"'-
11C.
413-4t6.
;-
l'
p:1',, _.
:;:
.::J \;. ;
949
&saatiol oncl Troce Ele011ents ;., liologicol Syste0111
Table 1U
A!>uncloncn of the el.n...ts
;, .... ....,.,......... nv.n.

andHOWOf...
ECH111's C'IVII
otoms/1 04 otoms Si
El......,t
Hydrogen
RMtrwoter
mgl- 1
1.119 )( 10'
Lithium
0.02
Beryllium
0.028
3
3
Boron
0.01
0.003
<I X ID-
0.01
1.2
Carbon
Nitrogen
Oxygen
474'
Fluorine
0.625
Sodium
Magnesium
Aluminum
'Silicon
Phosphorus
Sulfur
Clllorine
0.25<'
O,S<-.J
8.$6
1040
820
4. 1
0.4
4
0.02
3.7
10.000
32
8. 1
0.13
3.6
3020
Pocassium
Calcium
610
1040
0.48
120
0.022
Scandium
Tr.tanium
Vanadium
Chromium
S.1
1.326 )( l()l
O.OOSJ
IJ
0.01J
9"..8
1.987 X 104
2.3
416
us
Manganese
0.02S
o.oss
0.86
1.1
0 .11
0 .021
0 .024
6 X 10
0.031
0.070
O.OIS
O.OOIS
Gallium
Germanium
Atsenic
Selenium
0.0018
Bromine
0.002S
Krypton
Rubidium
X 1()-S
0.09
O.J7S
Strontium
Yttrium
0.033
0.165
0.02 -.
Zircoruum
Molybdenum . : . O.OOIS ,;. ->.

Tectu1et.ium- - -- - :
Ruthenium
I X 10-tw
Rhodium
2X
'
o.oos
0.01
1x
to
- 0.001
0.0002
- 0.02
0 .001
4.26
0.37
1.80
0.2 \' _.
......:.
,,
o.oso
0 .04
0 .003
., _0.001
4.22
I.S X
1()6
0.001
O.OOIS
0.00()6<1
O.OO:!J
O.OOJJ
8 X 1()-SJ
0.002
O.OOJJ
o.oo.s
3
IQ S
6 x 10-s
0.00:!3
0.00045
68
0.00021
0. 12
8.S
1.3 X IQ-S
2.6 x tO-
I X IO-
0.01
I X ID-'-
8 x . ID-"
'?'
6X
0.0018 .
:
!' .
9 x
", :..
0.0001
.S X 10-S
I X 10-7
10-7
2 x 10...._
J()-h
.i '; 8 x: t0'0:
0.67
0.0002
0.0003
1.3
0.07S
Zinc
-o.oos
17
1000
0.42
S6
Iron
Cobalt
Nickel
Copper
I.S
4 X 10
0.00)
0.001
0.001
2.64
2
0.135
0.1
O.!)j
10'
1.4'
0.00012
I.IOS >< 104
Argon
24
42
4.S
28
8.8 )( 10'
0. 1
24
20
82
282
I
0.26
10'
to-
0.18
6 )( 10- 7
9600
32.7
Neon
Indium'
1.078
1.2 x
Helium
Niobium
Oceon-er
mg L-
0.0001 ' '
...
- .. t
950
19 The Inorganic Chemistry of Biologi""l Systms
Table 19.4 (ContiJtU.J)
':?'-...... --
.-...----_...
. - .-
.. the eat1h's crust. riven.

andseo-ter"
Iridium
Gold
Mercury
Thallium
Lead
Bismuth
Polonium
Astaline
. .... ,.... ,,. .
Franc1UJ11
Radium :
Actinium
Thorium
, . . !.. ..,_
A . ..; . .. . . ''"to....
..
<.. Y.
J0- 16
6 X IO-IU
'r
.....
t ,
'
I X 10-ro.t.
Essential and Troc:e El...,ents in Biological Srsteoas
951
crustal abundances: Pb (0.08), Cd (0.0018), and Hg (4 x

The conclusion is
inescapable;
evolved UtiliVnf those elementS thDt WI!U obundont ond OVDi/Db/(' 10
it and
upon
Those elements that are rare were not used by
living systems because they were not available: n eithe r did these systems evolve
mechanisms to cope with them.
A closely related corollary of thls thesis is that many elements that are esunriol
when occurring at ambient concentrations nre toxic at higher concentrations (and. of
course, cause deficiency symptoms at lower concentrations). Interesting examples are
copper, selenium, and even sodium-all oceanic organisms are adapted to live in 0.6
M NaCI and our blood has been described as a sample of the primeval seas. Yet too
high concenltulioos of NaO are toxic through simple hypertonicity, i.e. , osmotic
dehydration. Selenium is a problem when it is either too rare or too abundant in the
environment : Uvestock grown on selenium-deficient pasture suffer from "white muscle disease": when grazJng plants (AstrOfDIIIs, "locoweed") that concentrate selenium from the soil. they suffer central nervous system toxinosis. Copper is essential
to many of the redox enzymes necessary to both plants and animals: yet too milCh
copper is severely toxic to most green plants.
There is an interesting group of trace elements. called ultrotroct' tlemenu because
they are oeeded, if at aD. at llO( more than I ppm in food. probably less than SO ppb.
These ultrotrace elements include
and nickel. certainly essential at these low
coocentr.ations, and cadmium and lead, probably 1101 essential. Many of these elements (e.g., Ni, As, Cd, and Pb) are quite toxic at any concentraOOn much above an
ultratrace level. Naturally. delermination of the essentiality of an ultratrace element is
even more difficult than for ordinary trace elements. an Ufe used and adapted to those
elements and those concentrations available to it (see next section). When humans
staned mining, using, and releasing these clements into the en' 'o nment. the ecosystem was faced with hazards it had nevet before encountered, and to which it had,
therefore, never adapted.
A slightly different view of this idea has been presented by t&ami, 1:3 who has
pointed out that the three em:yme systems in the most primitive bacterium.
Clostridium. are involved in electron transfer (e.g., ferredoxin), reduction of small
molecules
. nitrocenase). and hydrolysis (e.g . carboxypeptidase and carbonic
anhydrase). and employ. respectively. iron. molybdenum, and zinc. the three most
common tr,msition elements in sea water. It is postulated that these e nzyme systems
arose from protoenzymo:s thnt utilized these most common metals in primiaive seas.
One puu.le is copper, which is fairly abundant in sea water. and although it has been
thought to be essential for all organisms. apparently no requirement for it has been
found in strict anaerobes. Egami postulates that copper, with a positive stundard
reduction potential. was incorporated imo living systems only when the atmosphere
shifted from reducing (CH H1, NH,>to oxidizing (0 2). 11 This indicates the importance of considering changes that have occurred with time (including the advent of
'" Ad f\cures in 01oms pet 10.000 Moms silicon. For a disolulon or PI>. Cd. lind HB in llle envNa>mcol. in diel. and 1hcir 10xici1y, sec Choudury, 8. A.: Chandra. R . K. Pror. Fond Nu1r. Sri. t987.
m Nidsen. F. H.
IJS<I. 4, 2t.
19'15. 77. 1165.

'"' Su Broda. E. J. Mol. Evol. 1975, 7, 17. for a diwluiofto(lhis and relalcd questionsconcanitl&
o:> Epmi. F. J. Mol. Evol. 1914, 4. Ill: J.
""'
biosphere.
952
19 Th Inorganic Che.,;Siry of Biolovicol Systeoat
terrestrialism) and perhaps considering the microabundance of the various elementS in

d ifferent habitats.
Adaptations
t o Natural
Abundances 1 25
When the abundance of an element is unusually high or unusually low. organisms

develop mechanisms to handle the s tress. The first documented examples were the
presence of "indicator species" (plants) that 8fOW where soils contain an usually high
concentration of a metal. For example. the sea pink. Armeria maritima. has been used
in Nonh Wales as an indicator of copper deposits. In one extreme case, the drainage
from the copper deposits has concentrated in a bog to an extent of20,000-l0,000 ppm,
and the sea pink flourishes. Closely related Is the adaptation of various plants to
exceptionally high concentrations of various heavy metals in mine dumps and tailings.
Not only have some species adapted to extremely high concentrations of normally
toxic metals. but they have also evolved a high level of seJf.fenilization to pr-event
pollination and gene exchaJ18C with nearby populations that are not metal tolerant.
Some of tl1e c hemolithotropic bacteria discussed earlier in this chapter illustrate
these ideas. In undisturbed situations their habitat is extremely restricted. During the
process of mining, however,large surfaces o( the appropriate metal sulfide are aeated
and oxidized both in the mine and in the tailings with resultanl leaching. This creates a
favorable habitat for exploitation by the bacteria. One unfavorable result is the
lowering of the pH and the solubilization of metals, usually toxic, into the drainage
system. On the other hand, the isola.tion and selection of productive strains from such
sites. and their controUed apc>lic.alion. may lead to usef'ul biornetallurgic:al methods of
extraction of metals from low-grade ores (see Chapter 10).116
The hydrothermal vents discussed previously provide a pa.r.lllel. tu:lluraf environment with unusually large amounts of various metals-iron, copper. zinc-dissolved
from the crustal rocks by the superheated water. It will be of interest to learn how the
animals in the hydrothermal ecosystem have developed mechanisms to avoid toxicity
from these metals. Another source of possible toxicity, hydrogen sulfide, is somewhat
beller understood. Hydrogen sulfide is companble to the cyanide ion in its toxicity
towards respirntion. The vent organisms have evolved a variety of mechanisms to
prevent sulfide toxicity. One of the more interesting is that of the tube worm. Riflia
pachyptifu. Its hemoglobin has a molecul:lr weight of about two million, with an
extremely high affinity for dioxygen (recall that the vent waters are anoxic) and :1
second, high-affinity site to bind sulfide. This second site serves the dual purpose of
protecting the tube worm's cytochrome c oxidase from sulfide poisoning and protecting the sulfide from premature oxidation. Instead, both the dioxygen and sulfide are
transponed to symbiotic bacteria that metabolize them to drive the synthesis of ATP
and carbohydrntes. m
At the other extreme are adaptations to very low concentrations of a particular
elemenL We have already seen mechanisms directed towards the sequestration of iron
when it is present in small amounts. The ability 10 derrcr extremely small amounts of
an element can be a useful adaptation for an animal if that dement is important to it.
For example, hermit crabs recognize shells suitable for occupation not only by tactile
o:. Faraao. M. E. t. Fro11twn ill Bioii!D'II"IIic CJomrislq; XaKr. A. V. Ed.; VCH: Weinhrim, t9116;
pp 106-122. Octoiai. E.-I. c,,_,.JI'riltcipl, tl{BldrmohtT7 oftlw Elmwrrtr. Plenum: New Yor!<,
1!1117: pp J79-J9S.
,.. R<75si. G.
New Yen, 1990.
m O.ildress. J. J.; Fclbcclt, H.; Somero, G. N. Sci. Am. 1!1117, 2J6(S), 11}-120.
Bioche mistry of tf!e Nonmetols
953
stimuli but apparently also by the minute amount of calcium carbonate that is dissolved in the water around a shell. They can readily distinguish natural shells
(CaC01 ), calcium-beariJl! replicas (CaSO,J, and naturally containing calcium minerals
(calcite, aragonite, and gypsum) from non<alcium minerals (celestite, SrS04 ; modochrosite. MnC03; siderite, FeC03 ; and quanz, Si02).121fnasmuch as the solubility
product of calcium carbonate is only 10- 8 , the concentration of calcium detected by
the hermit crab is of the order of 4 ppm or less. Almost nothing is known about the
chemical mechanisms used by organisms in detecting various elements.
Biochemistry
of the Nonmetals
Structural Uses
of Nonmetalst2'1
Many of the nonmetals such as hydrogen, carbon. nitrogen. oxygen. phosphorus.

sulfur, chlorine. and iodine are essential elements, and most are used in quantities far
beyond the trace levels. Nevenheless. most of the chemistry of these elements in
biological systems is more closely associated with organic chemistry than with inorganic chemistry.
There are three important minerals used by organisms to form hard tissues such as
bones and shells. The most widespread of these is calcium carbonate. an important
structural eomponent in animals ranging from Protozoa to Mollusca and Echinodermata. It is also a minor component ofvenebrnte bones. Its widespread use is probably
related to the generally uniform distribution of dissolved calcium bicarbonate. Animals employing calcium carbonate are most abundant in fresh waters containing large
amounts of calcium and magnesium ("hard water") and in warm. shallow seas where
the panial pressure of carbon dioxide is low (e.g.. the formation of coral reefs by
coelenterates). The successful precipitation of calcium carbonate depends upon the
equilibrium:
Ca!+
+ 2HCO]
CaC03 +
(19.39)
and is favored by high (Ca2 +) and low (CO,). Nevenheless. organisms exhibit a
remarkable ability to deposit calcium carbonate from hostile environments. A few
freshwater clams and snails are able to build reasonably large and thick shells in lakes
with a pH of 5.7-6.0 anti as little as 1.1 ppm dissolved calcium carbonate.IJO
It is of interest that two thermodynamically unstable forms of calcium carbonate.
and vaterile, are found in living organisms as well as the more Stable calcite.
There appears to be no simple explanation for tho: distribution of the different forms in
the various species.
1issues containing silica are found in the primitive algal phyla Pyrmophyta
{dinoHagellnteS) and Chrysophyta (diatoms and silicoflagellates). One family of higher
plants. the Equisetnceae. or horsetails. contains gritty deposits of silica--hence their
'"" Mesce. K. A.
1982, 215. 991.
"'' Vincent, J. F . StntclltroiBiomouriob; Wiley: New York. 1982. WUcms, R. J. P. In Fronti<n in
Bioinorronic ClrC'111isrry; Xavier, A. V . Ed.: VCH: Weinheim, 1!18.S: pp 4)1-41. Webb, J.: Sl.
Pierre. T. G.; Dickson, D.P. E.; Mann, S.;
R. J. P. : Perry, C. C.:Grime. C. C.: Won, F.:
Runham. N . W. Ibid. pp 44t-452.
oo For a
of this point as wdl as ocher cxamples of orpnisms
limited conccl1lrations ofouoicnts, see Allee, A. C:: Emft'SOn. E. E.; l':ltk. 0.: Patlc. T.: Schmidt, K. P. Principles
of Animal Ecolov; W. B. Saunders:
t949: pp t64-167; pp 189-206. Pcnn.lt. R. W.
FreslrwaJor lnntt!bratt<S of tire Unitt!d
Ronald: New Vorl<. 1953: p 681; p 'I'QS(.
954
. ..
19 The lno<gonic Chemistry of Biological Systeows
...
,'\
.,
,.
...
name scouring rushes." Some PrO(ozoa (radiolarians), Gastropoda (limpets), ark!

Porifera (glass spoqges) employ silica as a structural component. Silicon is an essential
trace element in chicks and ratsllt nnd is probably necessary for proper bone growth
in all higher nnimals.
The third type of compound used extensively as a structural component is apatile,
Hydroxyapatite (X OH) is the major component of bone tissue in the
vertebrate skeleton. ll is also the principal strengthening material in teeth. Pattial
formation of fluorapatite (X "' F) from application of fluorides strengthens the strucand causes it to be less soluble in the acid formed from fermentil1! organic
material, hence a reduction of caries. Fluorapatite is also used structurally in certain
Brachiopod shells.
The suggested nntibiotic action of transferrin is typical of the possible action of several
nntibiolics in tying up essential metal ions. Streptomycin. aspergillic acid, usnic acid.
the tetracyclines. and other antibiotics are known to have chelating properties. PreAntibiorics and
Related Compounds su.mably some antibiotics are delicately balanced so as to be nble to compete successfully with the metal-binding agents of the bacteria while not disturbing the metal
processing by the host . There is evidence that at least some bacteria have developed
resistnnce to aniJbiotics through the development of altered enzyme systems that cnn
compete successfully with the antibiotic.m The action of the antibiocic need not be a
competitive one. The chelating properties of the antibiotic ma> be used in
metal transpof'l across membranes or to attach the antibiotic to a specific sile from
which it can interfere with the growth of bacteria.
The behavior of valinomycin is typic.al of a group known as " ionophore nntibiotics."tlJ These compounds resemble the crown ethers and crypt;ues (Chapter 12) by
having several oxygen or nitrogen atoms spaced along a chain or ring that cnn wrap
around a metal ion (Fig. 19.29a). These nntibiotics are useless in humans because they
are toxic to mammalian cells. but some of them find use in treating coccidiosis in
chickens. The toxicity arises from the ion-transporting ability. Cells become " leaky"
with respect to potassium. wflich is transported ucross the cell membrane by valinomycin. In the absence of a metal ion, valinomycin has n
different conformation (Fig. 19.29b), one stabilized by hydrogen bonds between amide and carbonyl
groups. It has been
that the potassium ion can initi<&lly coordinatt: to tht:
four free carbonyl groups (A) and that this can provide sufficient stabilization to break
two of the weaker hydrogen bonds (8). This provides two additional carbonyl groups
to cOordinate and cOmplete the change in conformation to that shown in Fig. 19.298.
Such a stepwise mechnnism would indicate that the whole system is a balanced one
arid that the reverse process can be readily triggered by a change in environment such
'-as at membrane;;u'!"ace or !f.there is a change in hydrogen bonding competition.
Medicinal Chemistry
"' Carlisle. E. M. Sci_.<' tm. 173. 619: F<. /'rue Frd. Am. Sx. -(p. Bit,/.
JJ. t7S8.
m Woodrulf. H. 8 .: Miller. I. t.C . Ia
ll!lribilun-; Hochstcr. R. t.C .: Quaslcl. J. H .. Eds. ;
Aadcmic: New Yo<lt. t96l; Vol. U. O..pttt 17.
w OclliaL E-1. G<'Mrol
.
of
of
l...anp, 0. A.: O..Toua. G. T.;

C. M. J. Am. .O...m. Sue. 1976. VJ. 12-12..
Elt'mrfllr. Plenum. New Yo<lt. 1987;
J. W. ; Rohrer, 0. C.; Weeks.
Md;c;nal Chem;stry
955
tl
(b)
Fi9- 19..29 IaI Molecular <ltuo:tun: uf

10 Ihe K. iuot. lbl
s 1ruc1urc ur Ihe fru
mol.:.:uk: . The .:11bvnyl
mutlc<'d A
free to
to K .
shown by
lines. with lhu-<.: marked 8 thought
to lle m\lst <uSCCf!lil:>lo: 1o br<akinc. (From Neupen-Luve<. K.: Dobkr.
Cllim -\rta
1975,
Smilh G. 0 .: Dlll1x, W. L: UliiJIS. D. A.: DeTina. G. T.:
J. W.:
Rohrer. D. C.:
C. M. J. Am. Clrrm. Soc. 1976, 97,
with
permi:ssion.l
The tetracyclines form an import;lllt group or nntibiotics. The nctivity appears to

result from their ability to chelate metal ions since the extent or antibacterial activity
p:u-allels the ability to form stable chel:ues. The metal in question awears to be
magnesjum or calcium since tho: addition of larae ::unounts of masno:sium can inhibit
the :mtibiotic effects. In addition, it is known thnt in blood plasma the tettacyclines
exist as calcium and magnesium complexes. us
w Umbo..
t..; DecockL.e Rtvhcnd, B.; l<umwski. H.; Bcru-. G. /ttO<f.
tM.Zl . 10111 .
9 56
19 T1te lno<vonic Chemistry of Biolovicol Syste ms
Chelate Therapy
We have seen previously that chelating agents can be used thera.,Wtically to treat
problems caused by the presence of toxic elements. We have also seen that an
essential element can be toxic if present in too great a quantity. This is the case in
Wilson's disease (hepatolemicular degeneration), a genetic disease involving the
buildup of excessive quantities of copper in the body. Many chelating agents have
been used to remove the excess copper, but one of the best is o-penicillamine.
forms a complex with copper ions
HSC(CH 3)zCH(NH2 )COOH. This c belating
that is colored an intense purple and. surprisingly. has a molecular weight of 2600.
Another surprising finding is that the complex will not form unless chloride or bromide
ions are present and the
complex always contains a small amount of halide.
These puzzling facts were explained when the X-ray crystal structure was done.tl6
The structure (rtg. 19.30) consists of a central halide ion surrounded by eight coppenO atoms bridged by sulfur ligands. These are in tum coordinated to six copperill)
atoms. rUJally, the chelat ingamino groups of the penicillamine complete the coordination sphere of the copperill) atoms .
As we have seen. the body has essentially no means of eliminating iron. so an
excessive intake of iron causes various problems known as siderosis. Chel:lting agents
are used to treat the excessive buildup of iron. In many cases the chelates resemble or
are identical to the analogous compounds used by bacteria to chelate iron. Thus
desferrioxamine B is the drug of choice for African siderosis.m The ideal chel:lting
Qs. 0cu'.
0 s.
Cu11
cr
tal
lbl
Fig. 19.30 Molecular llruCture of copper compex of o-peniciltaminc. The

ion: (a) the central cluster of Cu and liplina atoms only; (b)
the entire ion with the ccntr:tl cluster orienc<11 as in (a). [From Birket, P. J . M. W. L.;
Fra:mu. H . C .
Commun. 1,.,6. J/1. Reproduced with permission .)
'"' Birl<er. P. J. M. W. L.: Freeman. H. C.: CMm. Commlln. 19?6, l ll.

Andersca. W. F. In /nrx,:onic
;, Biolot> oltd Mtdklnr. ManeiL A. E.. Ed.: ACS
S)IJI1>05ium Series 140; American ChcnWcal Society: WasllinctOII. DC. 1980:
tS. Gonlatl<.
V. R.; Bacon. B. R.; Briltueam, G. M. AM. Rn. NIIIT. IM7, 7, 48.5.
U>
Chemistry
957
agent will be specific fQr the metal to be detoxified since a more genet'lll chelating agent
is apt to cause problems by altering the balance of other essential metals. The
concepts of hard and soft metal ions and ligands can be used to aid in this process of
designing therapeutic chelators. l
A slightly different mode of therapy involves the use of cis-diamminedichloroplat
inum(ll).
and related bis(amine) complexes in the treatment of cancer.
The exact action of the drug is not known, but only the cis isomer is active at low
concentrations. not the trans isomer. It is thought thai the platinum binds to DNA,
with the chloride ligands first being replaced by water molecules and then by a DNA
base such as guanine.l)9 Studies in vitro with nucleOiide bases as well as theoretical
calculalions .w indicate that the N7 position of guanine is the favored site for platinum
coordination . The cis-diammine moiety can bind to groups about 2SO pm apan. and in
vitro studies with di- and polynucleosides. as well as in vivo studies on DNA suppon
the hypothesis that the most important interaction is intrastand linking of two adjacent
guanine bases on the DNA chain by the platinum atom (see
19.31). 14 1The trans
isomer can bond to groups about 400 pm ;1p3r1 that approach the platinum atom from
opposite directions. and it is c hemotherapeuticall y inactive. The binding of cisplatin to
DNA would seriously interfere
the ability of the guanine bases to undergo
Watson-Crick base pairing. Thus when a se.lf-complementary oligomer {a ponion of a
DNA chain> reactS with the cis isomer, two adjacent guanines are bound and Watson-Crick base pairing is disrupted: 12
H!O
cir-(PUNH 3):CI(H!O)) +
a-
(19.-W)
A-p-G-p- G-p-C -p-C- p-T
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
(19.41)
T-p-c-p-C-p-G-p-0-p-A
For c/s-diamminedichloroplatinum{ll)to work according to the proposed mecha
nism. it must hydrolyze in tire ri11ht pluce: if it hydrolyzes in the blood before it gets to
the chromosomes within the cell , it will be more likely to react with a nontarget
species. Fonunately forthc
of the complex. the: blood approximately 0.1 M
in chlor-ide ion. forcing the h)drolysis equilibrium (Eq. 19.40) back to the chloro
complex. Once the drug crusses the cell membrane inau the cyoplasm . it finds a
' "'Pin . C. G.: Mattei. A. E. In

Cht mhlry in BioiOfy aJIJ Mtdkint, Mandt. A. E.. Ed.:
ACS SympoSium Series 140: American Clwnical Society: Washinsu>n. DC. 1980: Chaplet 17.
Butman. R. A. Struct. BortdM1 (8trlin} 1917. 67. 91 .
IJ9 The kinclics of lhis substitution I'Caelicn is disaluccl in Chapter IJ.
140
Mansy. S.; Chu. G. Y. H.: Ounan. R. E.: Tobiu, R. S. J . Am. CNm. S. l971.100.607. Basch.
H.: Krouss. M.: S1evens. W. J .; Cohen. D. / nor/(.

ttiU, 2$ , 634.
,., Shermaa. S. E.; l..ippanl, S. J . Clwm.
ml. Rudjilc, J.;
A. M. J.; van Oosterom, A. T.; van de Pune. P. StrJJcl . BonJillt(BtrliiiJ tm. 67, Sl. Fouls, C. S.;
Manili. L G.; Bynl. R. A.: Summers. M. P .;Zon. G.; Shinozulca. K . lfi4'R- Chtm. IMI.27. l66.
Lippert, B. Pr"f'. lnt CNm. 1m .17. 1-97.
141 Camdonna.. J. P.:
S. J. /ntHJl. Chtm. 19a. l7, 14$4. BNha. S. L: Toney. J. H.;
Uppo.rd. S. J . Prar. lnorz. Clttm.
J8, 477-516. Uppen, B. Prog. lnorr. Chtm. lm, .17,
t-97.
958
19 The lnorvonic Chemistry of Biological Sysums
6
HNL:;c
51
12
98/
N
lbt
PI
o,
eo
,..
Qc
Fig. 19.31 (o) Slructure of the cis-(NH,>:PI(dlp0p0)1 coq>lex, where d(pGpC) ; pwline
clwxyribose phosphate dinucleotide. (b) N1>mberi111 tyslem of sllalline to indicare N7. [From
Shcrmnn. S . E. ; Gibson, D. ; Wafli, A. H.-J.; Lippold, S . J.
lliSS.lJO, 412-4 17.
Reproduced with pcnnission.)
chloride ion coocentration of only 4 mM: Hydrolysis and subsequent reactions with
the appropriate biological targets can then readily take pl:x:e. t4l
An interesting aspect of the chemotherapeutic use of cis-diamminedichloroplatinum(lll and related drui!S consists of some negative side effects including nephrotoxicity. They are thought to be the result of the inactivation of enzymes by coordination
oC PI( II), like Hg(ll), to thiol groups. Application of the ideas of HSAB theory would
suggest the protection of these thiols by the use of competitive .. rescue agents that
have soft Slllfur atoms. These include the diethyldithiocarbamate, Et2NCS1. and
thiosulfate, S 20i-, ions.t44
Metal Complexes
as Probes of
Nucleic Acids
The coordination of cis-diammineplatinum(IJ) to guanine bases in DNA is only one

example of a large number of possibilities. The MgH ion has several imponant
funct.ions with respect to DNA and RNA structure and action. Nature has also
anticipated the chemist through the use cl "zinc finger" proteins as DNA transaiptional factors . They have a protein chain coordinaJed tetrahedrally to a zinc atom by
" 1 Martin, R. B. Ill Platinum. Cold. 011d Ollwr Mttol ClwmotlotrtlfHIIIic
ACS Symposium Sc:rios 209; American Chemical Society:

14-0
Lippard. S. J., Ed.;

DC, t98l; Olaplcr It.
See discussion by l.cmpus. E. L. M.; ltccdjilt, J. Adv. lMrt. Clwm. 1991, J7. 175-217.
Medicinal Chemistry
959
two cysteines and two histidines and provide specific structural infonnution for site
recognition on DNA.
Transition rneUll <:Omplexes may be used to probe specific sites on DNA and RNA
chains . Such internet ions may yield infommtion concerning the structure at those sites
or may induce specific reactions at them. On ly one exumple will be given
DNA helices are chirnl. They would thus be expected to internet with chirol metal
complexes in an enantioselective manner. This is illustrnted in Fig. 19.3:!. The intercalation of the 11 enantiorner of tris(o-phenamh roline)ruthenium(l l) into the righthanded helix of B-form DNAt-16 is more favorable than that of i\-(Ru(phenl,] 1 +. This
is a necessary result o f the internction of the orientation of the .. right-handed .. ligands
with the right-handed helical groove of the DNA. Obviously the chirnlity of the metal
<:Omplex is predominant in its interaction with the DNA. We
expect further
progress in the use of such enantioselective probes .
Lombdo
Ot llo
fis.
19.32 lllustr:.tioa of IRulphcnhf ..nontiomcn. bound by inlerc;,l:llton 10 B-ONA. The

A-enantiomer trillhl) Iii' easily inlo Jhe riJ;Itt-hnn.!c:.J helix. since the 211cill:lry lipnds an:
oriented alone the r\ahth:lndcd groovc. For the t\cnontiomer CleO I. in contrast. stcric
interference i.s cvidenl between lhc anciltsry l'hell'lnhroline lipnds :utd the phosph:Jte
backbone:. since for this lefthanded enantiomcr the: ancillary lipnds are
contnry to
the right handed eroove. (From Banon. J . 1<. : Oanishcfsky, A. T.; Gol<lberJ;. J. M. J. Am.
Clorm. Sm-. 19H4. 10.
Rcpr<>Uuccd with pcrmissiun.f
"''The: f'C2Jder's l>ltcntion is llr:twn to the: pnncrrln11 w0<1< in thi u= by

A. M.: ll:lntlfl, J. K.
t,.,. Jll. 41l-47S.
ll:vton: Pyle.
,.. A discussion of tile lltuelur<s of A. B. an<l Z DNA io hcyonll the SCOpe: cl this leal. Sec clitia the
rdercnce in Foocnote loiS or any modem biochcmiMry text.
We may thus end this chapter on bioinorganlc chemistry and this book on modern
inorganic chemistry by noting that a complex that Werner could have synthesized a
century ago (and resolved a short time later) is being used to answer questions that
neilher he nor his contemporary biolosists could have conceived.
Summary
It is true that many of the facts in this chapter were gathered by biologists. biochemists. and X-ray crystallographers, not o nly by inorganic chemists. But the interpretation of these facts and their further exploration falls within the realm of inofl:llnic
chemistry. Such factors as (I) alteration of emfs by complexation; (2) stabilization of
complexes by ligand field effects: (3) hardness and softness of acids and bases; (4) the
thermodynamics and kinetics of both "natural" and "unnaturnl" (i.e., pollutant)
species; (5) catalysis by metal ions; (6) preferred geometry of metal complexes; and (7)
energetics of (a) complex formation, (b) redox reactions. and (c) polyanion formation
come within the ken of inorganic chemists, and they should be able to contribute fully
to the future study of these system s. 1l1e effect is already being felt. Ooe need only
compare a recent biochemist.r y text with one of a decade ago to note the emphasis on
high spin vs. low spin metal ions, coordination geometry and configuration, and redox
reactions and thermodynamics.
The present convergence of physical and annlytical techniques combined with
inorganic theory makes this one of the most exciting times to be involved in this area
of chemistry. One can combine the hard facts and principles of our discipline with the
ever elusive yet fascinating mystery of life.
Postscript
"I say that it touches a man that his blood is sea water and his tears are salt, that the
seed of his loins is scarcely dilferenl from the same cells in a seaweed, and that of the
stuff like his bones are coral made. I say that physical and biologic law lies down with
him, and wakes when a child stirs in the womb, and that the sap In a tree, uprushing in
the spring, and the smell of the loam, where the bacteria bestir themselves in
darkness. and the path of the sun in the heaven, these are facts of first importance to
his mental conclusions, and that a man who goes in no consciousness of them is a
drifter and a dreamer, without a home Of any conUlct with reality. "17
Donald Culross Peauie
Problems
19.1 Why W8$lhecovalent rudius of the rMtal used on paae 891 instead of thai olthe +2 ion?
19.1 Why are tnniliCOI metals such as Mn, Fe, Co, and Cu needed in photosynthesis and
respiration rather than metals such as Ztt, Oa. o.. Ca?
19.3 Calculote the etlei'JY available from one photon o( liahl If wavetenam 700 nm. If it
generates a potential dilference
1.0 V, wlw Is the convmion efficiency?
or
Discuss how the use of

model systems can aid CM' undentanding of biochemical
systems. Is there any way they mi&ht detnct? ..
..,
D. C. An Almtuo /<>' Mo<kno3;
... Wq, J . H. Ace.
&1. 1m, J, 90.
Bostoa, 1!180; p t4
19.5 There ore two w:.ys in which

incrt":lSCS the energy uvailuble: (I) by usins
two lisht CDI)luring mechanisms. PS I and PS II ; (ll by Sl:lckins the chlorophyll in the
lfllJia Which are in turn stacked in the chloroplnst lsee Lehninser. A. L . Sci. Am ..
Se!>lembcr. 1961. for the st ructures). Which correspontls to hooking balleries in parallel
nnd which to hooking them in series'!
19.6
Common ions in enzyme systems are those that have loW site preference energies (from
LFSE) S&lCh as Co'. Zn' . and Mn=
titan Fe=, Ni 1 . or Cu1 . Discuss this
phenomenon in turns or the emalic hypochesis.
19.7
Discuss the proboble difference in the pockets present in c:ltboxypeptidase and carbonic
anhydrase.
19.8 The lo><icily or metols h:ls been variously correlated with th<eir (I) electronctllllivily;
(2) insolubility
the sulfideS; (J) $lllbilily or chelutes. Discuss.
or
19.9 Show how coordin;,tion r:J an 0: molecule to a heme StOUP can result in pairin& or the
electron 0111/w oxygm moln:lr when the bondins is
.. throuah a ,... bond
b. throuJ}t a lone pair
or unr oxyaen otom
19. 10 Oirrctions for the use or the antibiotic

advise apinst drinking milk or talcins
antacids with the medication.. In :tddition. w:u'llin&S are given concemin& its use (Leeth
may be mottled in couin cases). Suuestthe chemic:ul property or letl'llCyclinc thlll may
be involved in these dl'ccts.
19.11 Hi&h mcl"Cllr)' levels ioo temnol fuod chain ptedalors like tuna lish hove caused consida'o.ble worry. II has been round thut tU"" conlllin lurger thnn nvunge omounls or selenium. " " Oiscun the possible role
5elcnium with respect to the presence r:J
merc:.ury , t$1
.,r
19. 12 Although the hypothesis of Epmi may be .,. ovcr1implilication, it is ccrtoinly true thai
Fe2 ./Fe is widely used in redox systems.
in
estc:nfic.,tion . and similar
reactions. and molybt.lcnum in ni!roaenase. unthine oxidose. nitnue reductase. etc.
Puuins obundancc aside. discuss the specific chcmie:ll properties or these: meuls that
make lhem wdl suited ror their tasks.
z..:.
19.13 Carboxypeptidose A!Co=, noc only reluin$ the :>ctivity

AIZn')./t i
(l('lttally o
uctir ,nzymt. This being the cose. why do you suppose thai
is not
usoJ in the natur.ll sySiem?
19. 14 If you did
n<>t
answer Prol>lem 14.39 When you read Ch"fllcr 14. do su now.
19. 15 When pulicnts are treotct.l wilh t:>-penicilluminc for schlcrot.lcrmu. cystinuriu. rheumatoid
anhritis. and idillpalhic pultn011:1ry fibrosis. ):!"/ . show docrea.sed twae acuity (hypoaeusia). In eonua.r. only 4% or lhe patients beina t re:11ed with o-penicillomine for
Wilson's disea.'ie exhibit hypoceu>ia . Discuss u possible mechanism. How might the
hypoaeusio be treated'!":
,.., Fr.tUs!<Hia Silva. J. J. R.; WiUillms. R. J . P. Tltr

Cbtmi.rtry tl/ti,Eit"'rnu; Clarendon:
Oford. 1991; pP
'"'
H. E.; Goud'te. C.; Sunde. M. L.;
M. J. ; Wapcr, P.; Oh. S.H.; Hoc:bln.
W. G. Sd<nn- 1m. 17J. 1122-1124.
Oocn. R. W.; wt.un&er. P. 0 .: Weswia. P. H.
Clt.lm. 19'15,4. llS-Ill. Schnt.ner. G. N.
Bl<>i""'l Cltcn1. 191'6. :U. Z7S.281. Mouumoco. K. Ia Biolo/lkol Trocr Elrmr11t Rr.rorclt;
Subramani:ln. K. S.; lycnpr. G . V.; Clbmoto. K.. Eds: ACS Symposium' Sc:ria
Chemical Society: WashiQ81011. DC. 1991; Cha!>l<:r 22.
u> Henkin. R. 1.; lindley. 0 . F. l'roc. Not/. AC#d. Sci. U. $ . A. Ill&). 62. lO.
t"
962
19 The lftorganic O.emistry of Biological Syste"'s
19.16 Predict which way the fdlowina equilibrium wiU lie:
Hb + Hb(O,),
(19.42)
2Hb(0zh
Explain.
19. 17 Althouah sickle cdl anemia causes problems in many oraan syslms. the chief cause cl
de:uh of children with SCA is bacterial infection. Discuss.
19.18 Usins the reducdon emrs aiven in Appendix F, construct a Latimer dia&fnm, complete
with skip-step emfs for one-, two-, and fou r-electron reduction ol oxygen to supcroxide,
peroxide, and hydroxide. Discuss the bioloaieal "snificance of these emrs. Recall that a
livins ccU is basically a reduced syslm threaJened by oxidizing aaents.IJJ
19.19 Biochemists tend to speak ol"dismuration reactions" such
as:
(19.43)
that are catalyzed by

dismutos, . What term do inorganic c.h emists use for this
phencmenoo? What type of metal do you suppose is in superoxide dismutase?
19..20 Gray and cowod<en',. have
coppcr111) catboxypepcidase A. Cu"CPA, 1nd
comp=cl ita spectrum, that
the enzyme with iahibitor
and those
seven!
other copper111) complexes with nifro&e" aftd oxyacn liptina aiOITl$. Some or these data
together with tbc seomerry about the copper icn are:
or
Set
or
c1 rogalftog atoms
N,N.N,N
19,200-19.600
t4,100-17
ll,900-t4.700
.soo
N , N ,O, 0
N.N, O,O
o. 11o. o.o
13.500-IS,OOO
Cu CPA:
N, N . 0. 0?
Cu11CPA JIW:
12..$80
N,N,O,O?
11.400
These are the four atoms in the coordinalion sphere o( the

ccpper{JI) ion.
JIPP is
l\.
n.
IJI
inhihitor o( cart>oxypcptidasc
Accou111 for the treftds in the velues of .... in the first four rows of the table listing
6terature vlllues ancJ known geometries.
11
b. Predict the geometry of the liaatins atoms uboul the Cu" ion in Cu CPA and in
Cu 11CPA j!PP.
c. Comparina the values cl ..... or Cu11 CPA with and without lhe inhibitor present.
suaaest what effect the inhibitor may be havina on the geometry or the copper ion.
19.21 For simplicity the
interxtion in myCIIIobin and hemosJobin (but not
hemerylhrin) was discussed in tenns or neutral oxyaen molecules bind ina to Fe 11 However, much or the current
discusses these phenomena in terms or superoxo ond
peroxo complexes and one sees Fe111
Diseuss what these formulations and terms
mean, and describe the related
in terms or charaes. electTon spins. etc. '"
o;.
Fridovich. I. Am. Srl. 1975, 61, S4.

,,. Rosenberg. R. C.; Root. C. A.; Bcrnswn. P. K. : Gray, H. B. J. A"'.
2092-2096.
Ul
U>
.... Sc>c. 197S. '17,
Vaska. L. Ace. Cllnn. Rrs. 1976. P. 175-181. Rd. C . A.; Chcui1C- S . K . Ptoc. Nllll.l:od. Sri.
U.S.A . Jm, 74, 1780.
111.n
Using your knowlc<lKe of periodic relatiOMhipS. pc-edict which dc:rnc111

come
closest to reproducina !he: behavior ol molybdenum in niarogcnusc. Rtt:lll tlwl nitrogen
ftxntion invdves both comptualion and redox re3ctions.'
19.23 In order to study lhe function o1 oxyaen binclina by myoQiobin and its effect on muscle
function, Cole (Footnote 16) perfused an isolated muscle with hydrosen peroxide. Why
did he do this?
1!1.24 Discuss each of the foUowinJ situations:
a. One
cac:ountered in the manufac,ture and preservation of H:O: is its
laneous decomposition:
2Ht0t -
2H:O +
0:
which is exochermic (tJ.H -t96 kJ mol- 1) . To reduce this decomposition. COJli'Cf'

ions nre care!lilly excluded or chclntcd. "'
b. Nature's pc-OCcclion a&ainstthe dcslructive oxidative powers o( H,O: nre the enzymes
C:llalasc and peroxidAse. both ol which contain iron.
e. Superoxidc, o;-. is pcr11aps even more dan&crotJS than hydrog.., peroxide u an

oxidaat om! free radical, thouah olhei'WISC somc:what similar.
d. Supcroxidc cfisnwtasc contains both zinc and C09JICI'. Zinc may be replaced by CD(II)
and Hg(U) and lhe m z:yme retains its activity; no
of copper with retention
ofactivity has yet been found. Discuu. !Hint: You con discuss lhis on
rom the most ollhand
10 a quontitativc: dcmonsu:uion Mth numbers.
Oloosc aa appropriate levd (or ask your pc'olessul) ancJ altack the problem
accordina]y.)
e. Procaryotcs have a primitive S<Jpcroxidc dismutase with a metal olhcr thon copper.
Suaacst possible met;>JS. ,,.
1!1.25 If you did not work Problem 12. 16 when you read Clwpter 12. do so now.
1!1.26 Fc<OH): IK., = 1.8 x tO- " t and fe(OHJ, (K, 2.64 x to- "") have serendipitous
solubilities: If one can rermmbcr the cxponcnu, one cun " in.stllntly" eslimate the pH
ncccssary to make a I M solution ol
or Fe,. .
a. Explain. What arc the
pHs of these solutions?
b. Calculate lhe exact pHs a5.umift1! ideal behavior.

19.27 Bcz:korowiny
illnesses.
scver-1
u
inllic:uinll relluec.J iron obwrptiom lluri"!! fehrilc

for lh( ncJ;,ptivcncss of SU<h an cfi'C!Ct .j
19.28 ..t,ci.t ruin has been dcftncd us 11ny pf<cipll:otlon with u pH lower tlun S.6 . Why $.6 inste:.cl
d 1.0? Can you paform a CAlculation to reproJuce this vn lue'1

19.2!1 Exploin what effect uci.J rain would have on lhe condition of each d 1he following. and
why:
a. The Ti\i Mahal, at Acro1, India

b. A limestone bam ncar Antietam Balltctleld. Maryt2nd . !Jarina from the Civil War
e. 'The Karyatidcs. lhc Acropolis, A!hens. GreeCle
"'Sliefi:l, E. I. /'roc. Nool. Acod. Sri. U.S.A. 197J. 70, Wll.

on Crarns>looo. C. A. ; Faber, G.; Jones. R.; Lenw:r. J. P.; Schcllc, S. In 1M MoJ<!<11 1-nic
Cikmicms /lldUJtrr. Thoii1'SQII. R.. Ed.: Chcmic:ll Soeicty Spccill Pullicalion No. l l ; Chemical
Sociely: London. 1977: p 2A4.
""Fridovich. I. Ad. /norg. Bioclwm. tm. I. Q , f r.!WiiO-da Silw, J . J. R.; Wiliams. R. J. P. 1M
Bioloficol Cltnrri6trJ u/ tlw Ehrrwnrs; Clarendon: Oxford. 1991: pp 337, 383. J9S-J96.
U9
of Nonhr-lron; BcUC<oveiny, A .. Ed.; Plenum: New Yotlc. t980: p 90.
964
19 The Inorganic Chemistry of Biological Systems
d. The asbestos roofS on the authors' houses in Cdkge Part. Maryland. and ChnJ1eston,
lllincis
e. The integrity d the copper and galvanized aed eaves-troughs and
on
those houses
f. The integrity of the brick und sandstone siding of those houses
g. The growth d auleas planted along the foundations of those houses
h. The integrity of the aluminum siding on a neishbor's house
I. The slate rod on anolller neiahbor's house
J. The
d galvanized steel fencing in the neighborhood
k. The ability or an aquatic
10
form its shell in a lake in the Adirondack Mountains
1!1.30 For each d the above for which you predicted an adverse etfect, speculate as to the
likelihood thut the.re actually will btt an effect, i.e., whether there will be acid min at that
p;:u1iculur socraphic site or not.
1!1.31 Page 936 refers to "the ruSIred soils d Oahu." What is the chemical origin or the ' 'rust
red" color? Wha1 is the physical source of the color?
J9.3Z Niebohr and Richardson have written on extremely interesting anicle entitled, "'The
replaCement of the nondescripr tenn 'heavy metals' by a biologically and chemically

significant classifiCJllion of melal ions... Their abarad states, in part:
It is proposed that the term "heavy metals" be ubandoned in favor of a dassificalion

which separates mews . accordins to their binding preferences . related io atomic
properties.... A review of the roles of metal ions in biological systems demonstrates the
potential of the proposed classification for interprelina the bioc!lemical basis for metalion
toxicity
Discuss in terms of the suggestions provided by the obstruct. Propose a theme for the
Niebohr/Richardson article (as thoush II were your own) and give some illustrative
examples.t60
19.33 Review your knowledge of coordination chemistry with respect to nomenclature: Why is
the moleade shown in Fia. 19.27 the "6" i.somer?
19.34 The paralldsm of sunlil!htdriven photosynthesis/respiration and the chemotithotophic
oxidation or sulfide and sulfur by bacteria (page 890), as well a.' the possibility of metal
other problems and
toxicity near hydrothermal vents (page 952), has been noted.
poSSible solutions 10 be expected from hydrothermal
organisms. 1M
1!1.35 If you did not work Problem 12.34 when you read Olaper 12. do so now.
19.36 Bioinorpnic compounds tend to change structure (bond lensths and bond anaJes). mo<e
or less. upon chanaes in oxidation stale or coordination number. The spectrum runs from
blue copper proteins (almost no changes) to hemoglobin (considerable rearrangement).
Discuss the chemical reasons for these ditferenc:es in behavior and how they affect the
biologic:al function of these moleCllles.
19.37 If CO and e - N - are isoelectronic, why does hemoglobin (Fe>+) have the Slronger
but methemoglobin (Fe1 +) binds CaN- more tiahtly? (Hint:
interaction with
Compore Fe11 -CO. Fe111
Fe11 -CN-. and Fe111-CN-.)
c- o.
-co.
19.38 At pH 7.8, the structure of reduced (Cu1) plastocyanin has a structure very similw'to thai
of Cu11 plastocyanin
19. 1S) except for small dilferences in bond lengths. AI. pH 3.8.
the copper is lripally coordinated with the founh interaClion (Cu-imidazole) broken.
Predict and discuss the redox activity of plastocyanin as a function of pH .
160 Niebohr. E.; Richardson, O.H. Environ. Poliut. Stri 81980. / , 3.
161 t::hildress. J. J .; Fdbeck. H.: Somera. G. N. Sd. lvnl!r. 19111. 256tn.
A.pptndix
A
The Literature of Inorganic Chemistry
T he
is not meant to be 11n exhllustive list ofall of the books of interest to an
inorganic chemist, but it is a short list of useful tiUes.
Texts and General Reference Books

Butler, I. S.; Harrod J . F. lnorgank
jamin/Cummings: Redwood City. CA. 1989.
and Applications; Ben-
Chambers, C.; Holliday, A. K. Inorganic Clrtmistry, Bunerworths: London, 1982.

Cotton. F. A.: Wilkinson, G.
Inorganic
Sth ed.; Wiley: New
York, 1988.
Cotton. F. A.; Wi lkinson. G.; Go us. P. L. Ba.fic lnurga111'c Clrmtistry, 2nd ed.; Wiley:
New York. 1987.
Douglas. B. E.; McDaniel. D. H.: Altxander. J . J . Cnllt'cpts a11d Mmlels
Chemistry.
eel.; Wiley: New York. 1983.
Greenwood. N. N.; Eam.s haw, A. Clu:mi.ftry of
Elcnll!nrs; Pergamon: Oxford.
1984.
Jolly. W. L. Modern lnorgant'c Ch,mistry, 2nd ed. ; McGraw-Hill: New York, 1991.
Miessler, G. L.: Tarr. D. H. lnorgallic
NJ. 1991.
Prentice-Hall: Englewood Cliffs,
Moeller. T . Inorganic Ch,mfstry: A Modern lntruduction; Wiley: New York, 1982.

Porterfield, W. W.lnorranic
ing, MA. 1984.
A Unified Approach; Addisoo-Wesley: Read-
Purcell, K. F.; KoiZ, J. C. An Introduction to Inorganic
Saunden;:
Pfliladelphia, 1980.
Sanderson, R. T. Simple Inorganic Substanas; Krieger: Malabar, FL. 1989.
Sharpe, A. G. Inorganic Chrmistry, 3rd ed .; Longman: london, 1992.
A-1
A- 2
A The llleratw. of Inorganic Cheoaislry
Shriver, D. F.; Atkins, P. W.; Longford, C. H. lnorgunlc Chemls/ry; Freeman: New

York, 1990.
Wulfsberg, G. Principles of
Monterey, CA, 1987.
lnorgunic Chemistry; Brooks/Cole:
Classical and Comprehensive Reference Works

Comprehensi11t! Inorganic Chemistry; Bailar, J . C ., Jr.;
H. J.; Nyholm. R.;
Trotman-Dickenson, A. F., Eds.; Peraamon: Oltford. 1973.
MTP l nteriUJtional Review of Science: Inorganic Chemistry, Series I;
H. J.,
Ed.; Butterworths: London. 1972.
Gmelin , L. Handbuch der anorganischen Chtmit; Vertag Chemie: Weinheim.
1924-1991.
Dictionary of Inorganic Compounds; Macintyre. J. E., Ed.; Chapman & Hall:
London, 1992.
Comprehensive Coordination Clremi>try: Wilkinson. G.; Gi llard. R. D.; Mc<leverty.
J . A ., Eds.; Pergamon: London. 1987.
Comprrhensive 0rgGIIOtMtall/c Chemistry; Wilkinson , G.; Stone. F. G. A.; Abel.
E. W ., Eds.; Pergamon: Oxford, 1982.
Append
B
Units and Conversion Factors
The International System of Units (SI)

Slbaoaunils
s,....,.,.
Physiaal..-;ty
Unit
Length
me1e1
kiJosram
second
ampere
kelvin
mole
candela
c:d
Mass
Time
Electric currenc
Thermodynamic tanperacure
Amount of slJbstance
Luminous inlcnsity
ka
s
A
K
mol
Common cleri.ed units
Physical quCIIIity
Frequency
Energy
Force
Pressure
Power
Electric charse
Electric potential difference
Electric resistance
Electric capacitance
Ma11ndic: ftux
lnduaance
Magnetic ftux density
I,M;.
joule
newton
p-.tscal
watt
coulomb
volt
ohm
f.lrad
weber
henry
lesla
Symbol
O.IWtioft
Hz
s-
J
N
Pa
J m-
w
c
v
n
F
Wb
H
T
k& mt s- 2
N m- 2
J s-
As
J ... - s-
V A- 1
As y-t
Vs
V s A- 1
Vs m- 1
A-3
A4
8 Unitt and Coft,.rsion Factors
!Talixes
.....nx
s,.,bol
auo
fcmpto
pico
nano
micro
milli
ccnli
10- 11
10-u
10- 12
10-
10- 6
10-3
10-2
JL
deci
deka
o-
mega
da
h
k
M
sisa
hccro
kilo
tera
pcta
T
p
exa
10
lol
Ia'
10'
1011
1012
101s
10"
Physical ..,c1 cf..,lcal canst-...

Elccrronic charge
c = 1.6021m3 x
Pllli!Ck <:onstant
Speed eX light
Rydberg <:ons tOllll
Boll.zmann constalll
Gas constunt
Avogadro number
Faraday constant
Electronic rest ma.ss

Prolon mass
Bohr radius
6.62fHISS
o- c
10-M J s, 6.62601SS
of vacuum
Pi
Base. noturol logarithms
10- n erg s
2.99792.5458 x lei' m s-
1.0973131S34 x io' em-

1.380658 X 10- 23 J K- 1
R : 8.314S70 J K- 1 mol- 1
N,. = 6.0221367 X l<r' 11101- 1
= 9.6485309 x 104 C mol- 1
me = 9. 1093897 X 10-21 g
m, = L672623 x ro-z g
Do = S2.9lnl249 pm
24
P.B = 9.274096 X 10"" A
9.274096
10-11 erg p uss-
11 2
o = 8.854187817 x 10"" C m- r'
err;
Bohr magneton
Pcnnitrivity
h =
c =
R =
k =
"= 3. 141S926S36
= 2.71828
QU<Jntitits, Un/1.1, and $yn1bols in Pl1ysln>J Clwmlstry, t988; MUtt, I. M., Ed.; Bllo<:kwcll
Scientific: Oxford, t988.
Conversion
lacton
NMtiply
length
em
em
by
to'
107
10 10
em
}..
roo
to obtain
;.
nm
pm
pm
Energy
kcal
mot-
eV
Quantitws, Units.
I. M., Ed.;
4.184
96.49
in Physico/
Sclcnlilic: Oxford. 1988.
kJ
kJ
mor'1
mor
1988; Mills.
I Units and Convenion Factors
A-S
Convonion factOt"S (Continu.J)

Multiply
erg
wave numbers (cmkJmor'
ev
Dipole moments
Debye
Cm
Pressure
atmosphere
mm }-lg (torr)
pascal
pascal
to obtain
by
to- 7
1)
t . t962
S3.S9
23.06
3.)36
0 .300
to- 3
X 10- )U
kJ mor 1
em-
kcal mol"" 1
em
loW
1.0 t3
t33.)
10S
9.869
7.SOI
to-
to- '
Pn
Pa
:lim
mm Hg (torT)
Notes
Sl uni.ts are obviously going to diplace older syscems and units. We must all familiarize
ourselves with them. Just as obvious is the fact that this displacement is going to !<Ike
time. and the contemporary literawre is
to e xhibit a variety of units. lllercfore.
this book h:ls tried to take a middle course: To repon all values in S l or 51-derived
units but also to include frequently that same volue exp ressed in "tmditional" units.
We realize that by so doing, we run the risk of being " neithe r fish nor fowl. and of
alienating burh the progressive. who would like to see 1000/. S l. and the conservative.
who would like to stick to the cgs system. Nevertheless. the decision must be based on
consideration of the students as future c hemists who will encounter kilojoulc5, kilocalories. eledron volts. picometers. nanometers. anastroms. coulomb meters. and
De byes; they had better have some familiarity with each of t hese units. The irony of it
all is that the easiest c hange to make and the one that causes no confusion wha tsoever is that of angstroms to picometers: I A - 100 pm. No one is
to confuse
a bond length of Au-Au = 300 pm (in the unusual gold compounds of Chapter 18)
with Au-Au = 300 A. once huving observed tha t molecular dimensions are
ITll!llSured in angstroms and
of picomcters. Yc:t th is change seems 10 be the
last that will be made: Crystallogruphcrs h;10g on dOIJilCdl y to the: convenient units
of angstroms . On the other hand. kilojoules seem to be replacing kilocalories at a
reasonable rate. This means that old values. learned in passing. as kcal mol"" 1, are
being supplemented or replaced by new values as they are reponed in the literature.
sometimes kJ mol- 1, b ul more often still kcal mol- 1 Recently. one of the authors was
asked in class abou t the Au-Au bond energy in the compound mentioned above. He
was sure that it was 30. but 30 wh:ll?(!) The factor of four between kaojoules and
kilocalories is just small enough to make the CXlnfusion of units easy and. simultaneously. large enough to be diSllstrousl [Do you think that the Au-Au bond
mentioned above has a bond eneray of 30 kJ mol- 1 or 30 kcal mol- 1? Make a
prediction and check it in Chapter 18. Does knowing that it is in the range of strong
hydrogen bonding energies help? Sometimes mnemonics like that help-they saved
the aforementioned author's skin!)
fn view of this entropy that c hanajng from one system to another entails. the
following suggestions are made to those familiar with older u nits and trying to get a
"fed" for Sl units. Many readers of this book will have encou ntered essentially only
A-6
I Uaits aad Caannion Fac1an
Sf units in their education-they may wonder what all of the
is about. They will
knnov as soon as they stop reading textbooks and start reading the original literature!
Length, molecular dimensions. As mentioned above, this surely is the easiest

conversion to make. Bond lengths in picometers are exactly 100 times greater than
when expressed in angstroms.
Enugies. Ionization energies expressed in kJ mot - are approximauly (Ji"X. errOt")
100 times greater than when expressed in electron volts. Bond energies in kJ mot- are
approximately (4f'X. error) four times their values in kcal mor ' .
The calculation of lauice energies (and other Coulomb's law energies) is complicated somewhat by the fact that In S l the permiUivity (dielectric constant) of a vacuum
is no longer defined as one but has an experimentally determined value. Furthermore.
for reasons we need not explore at present. Coulomb's law is stated in the form:
= q,
X q.
41TU
(B. I)
The calculation may be simplified if the values for

and " are included in the
conversion f.lc:.tor. 1.389 x
kJ mot- pm (the reader should confirm this value),
which allows direct calculation of the tau ice energy using ionic chaf"!les and distances
in picometers.
Dipole moments. The differences between the two systems are such that there
appears to be no simple corrdation. Nevertheless, since most Sl tables will probably
list values as coefficients of 10-.lO the followillll mnemonic: and rule of thumb should
help: To get Sl values from Dt'byes, divide by 0.3.
Prrssure. Fonunately, an atmosphere is almost (1% error) toS Pa. So a standard
atmosphere is about 100 kPa. and when high pressure experiments are presented in
terms of GPa, each gigapascal represents about 1()4 atmospheres.
Append
c
Atomic States and Term Symbols1
The energy of a spectral transition for the hydrogen atom is given by the Rydberg
formula:
" = 109.737 em- (
-'nz1 - -'n:2!) wlrt!rt' n
> n1
(Cl)
which consists of two terms. II is common for

to apply the word tum
to the enugit's associated with the states of an atom involved in a transition. Term
symbols are an abbreviated description o( 1he energy. angular momentum. and spin
multiplicity of an atom in a particular Slate. Allhough the inorganic chemist generates
the term symbols used from knowledge of atomic orbit:! Is. the historical process was
the reverse: S. P. D. and F stares were observed spectroscopically . and named after
sh<1rp (S - P), princ-ipal (P - S), diffitu (D - P). and fimdumenrol (F -+ D)
characterislics of the spectra. Later the symbols s, p, d, andfwere applied to orbitals.
Atoms in S. P. D. F . .. states have the same orbital angular momentum as a
hydrogen atom with its single electron in an .f. p. d.f, . . . orbital. Thus we can define
a quantum number L. which has the same relationship to the atomic stale as I has to an
atomic orbiM (e.g .. L = 2 tlescribes a D state). L is given by:
(C.2)
We can also define I he component o( the total angular momentum along a given axis:
M,_ = L. L- I, L - 2 .. . 0, . . , -L
The number of possible values of M ,_ is given by 2
m 11 + m11
M,_
(C.3)
1. M ,_ is also given by:
+ + m1
(C.4)
Likewise we can define an atomic spin quantum number represenlifl! the total spin:
I
I Few a n ellen>ive discusoion of 1erms. symbob, and Sillies, see Gatoch. M. Orl>itob,
Wiley: New Yodt. t986.
llt!d
A-7
A-8
CAtomic States and Term Symbols
For a given value of S, tha-e will be 2S
+ I spin states characterized by M 5 :

(C.6)
= S. S - I. S - 2. . . , -S
or
(C.7)
Now the total angular momentum of an electron is the resultant of the orbital
;mgular momentum vector and the electron-spin angular momentum vector. Both of
these are quantized, and we can define a new quantum number.j:
j = l+s
(C.8)
Since .r "' :!: I. it is obvious that every value of I will have two values ofj equal to
I + ! and I - l. The only exception is I = 0. for which j = :!: !; these values are
identical since it is the absolute magnitude ofj thai determines the angular momentum.
We can now couple the resultant orbital angular momentum (L) with the spin
angular momentum (S). The new quantum number J is obtained:
J = L + S. L + S - I, L
+ S - 2, . .. !L - S1
(C.9l
The origin of the J values can be seen from a pictorial representation of the vectors
involved.-
L=l
S=l
1=2
L= l
L:2
L=2
S=l
S=l
J =3
1=1
S=l
1=0
The number of J values available when L > S will be equal to 2S + I, ami is

termed the nwlliplicily of the state. In both of the examples pictured above. the
multiplicity is three. The multiplicity is appended to the upper left of the symbol of
state and J to the lower right. The above examples are thus 1p and lO states
(pronounce<.l "triplet P" and "triplet 0"). The individual terms are 3P2, lP1 , and lP0
(left), and J01 , JOt, and 300 (right).
When L < S, the series in Eq . C .9 is truncated (note the absolute magnitude
symbol in the last term) and there are only 2L + I values. An example is the nst
configuration, where L = 0 and S = i; J can have only the single value of +P
: Oe.pite the foc:tthere is but a single value of J far the ground state of hydrogen. spec:trO<COpi.<ts wrile
its term symbol as 2S112 The rc:>son for thl< is that transitions between >late< of dill'c:rcnt spin
muhiplic.itics are spin
thus transilions from a spin-paired sinakt I such as 'Sl 10 a
unpait<:d triplet t>S) are not allowed. Howev..-. with hydrogen (unci the alkali melals os well) the
sround state has an
electron. and transitions 10 doublet sLtcs with " sinaJe unpaired
electron are allowed. For ease in noting which transitions are allowed and which are pin forbidden.
spcctroscopiSL wrile 2S. thoush a<lmiucdly it can lead to confusion.
C Ato ... ic Stots o11d T. ,., Sy...bols
A-9
To turn again momentarily from the abstractions of orbitals and quantum numbers
back to the spectra that generated them, consider the transition from a Is orbital in
hydrogen to a 2p orbital. The terms and transitions are:
The zplf2 term lies slightly higher in eneray than the 1P1n, and therefore the spectral
line is split into a ''doublet"; hence the or\sin of the usage. It may be noted that
in respect to these transitions the following selection rules operate: tl.n. arbitrary;
tl./ = I; Aj c 1. 0.
Assig ning Tenn Symbols
We have seen that the 1enn symbol for the ground state of the hydrogen atom is 25m
For a helium atom L .. 0. s = 0, J 0, and the term symbol for the ground state is
For an atom such as boron, we can ma.ke use of the fact that all closed shells and
subshells (such as the He example just given) contribute nothing to the term symbol.
Hence both the ls2 and 2s2 elttt rons give L - S J - 0. The 2pl electron has L = I,
s c f. and J .. I l. yielding 2P1n and 2p)I! For carbon there are two p electrons.
The spins may be paired or unpnired. soL 2, I. 0; S = I, 0: and J = 3. 2. 1. 0. To
work out the appropriate states fo r this atom requires a systematic approach. Note.
however. that when neon is reached we have again a IS0 : sodium rtpe;lls lhe 25 112 ,
magnesium S0 etc.
s.,.
A Systematic Approach to Term Symbds

In Chapter 2 it was shown how m1 and m, values could be summed to sive MLand Ms
values to yield terms for the pectroscopic states of an atom. If there arc two or more
electrons. it is usually necessary to proceed in a 5ystema tic fashion in gener:uing these
terms. The following is
method of doing so. The p2 confisuraaion of carbon is
used.
I. Dt!rl.'rmin<'th(
val11es of ML aml M s For the p2 configuration, L can
have a maximum value of 2 and ML can have values of - 2, - I, 0. + I, + 2.
The electrons can be paired (Ms .. 0) or parallel (Ms .. +I, -I).
2.
electron configurations that are allo ..

by
Pauli princi
ple. The easiest way to do this is to draw up a number of sets of p orbitals as
in Fag. C. I (each venic31 column represents a set of three p orbitals) and fill in
electrons until all possible arrangements have been found. The M L value for
each arrangement can be found by summing m 1 and Ms from the sum of m,
(spin-up eltttrons have 11/tlitrarily been assigned m, s +U. Each
consists of one combination of M, and Ms.
3.
up a chort of microstates. For example, the microstate corresponding to

the first vertical column in Fig. C . t has M, +2 and Ms = 0. It is then
entered into the table below under those Vallie$. Sometimes the mt and m,
A- 10
C Atomic Stotoos and Tna Symbols
,.,,.
+I
'"
0
-I
"
)Is
Fig. C.l The
t0'
"
'' ' ' ' t ' ' '

t t
t t
t
t t
"
"
'
' '
0
t t
microstares and resull:lnl values of M, and Ms f01 the ls"ls>:!p' cltron
eollfigur.>tion or easboo.
values are e.l 1led directly into the table,J but if the electron configurntions
have beeo carefully worked out, there is no need of this. The fifteen microstates ofpl yield:
Ms
M,_
-2
- I
0
+I
+2
+1
X
X
X
X
XX
XXX
XX
X
-1
"
X
X
4. Resolve the chart of microstates into appropriolt atomic stall's. An atomic

state forms an array of microstates consistins of 2.$ + I columns and 2L + I
rows. For example, alP state requires a 3 x 3 array of microstates. A tDstate
requires a sinsle column of Sand a 'D requires aS x S array, etc. Looking at
the arrays of microstates, it is easy 10 spot the unique third microstate at M L =
0 and Ms = 0; this must be a IS. A centrnl column of M 5 0 provides a 'D.
Removing these two states from the table, one is left with an obvious 3 x 3
array of a 1p state.
M,
0
_,
It
"
It
It
+1
M,_
-2
- I
0
+I
+2
It
>To ensure !hat all microslalea hAve been written. !he lOIAI number N. of rnicrosuotes asoociatcd with
an cleclronic eonflautation, /It, havll\a electrons in an orbical sa with "" azimutl\.11 quant...,
number. /, is
No
Nt!
wha'e N, - 2 (21
(Cto
1), the IIUIIIba of m1, m,
(Frum Condon. E. U.; Shonley, G. H.
Cambridae.
1963.)
combi1131ioN ror a Wlrk electron in ohe orbital sa.

Tlwory of Atomic SM<frtJ; Cambridce University:
C A1ooaic Sloles o11d T....,. Symbols
___'_s___ _ - - - -'s_o_
A-11
: o64&.4
I
I
I
I
I
I
I
I
I
I
I
I
I
o.
'D
, , . - - - - - - - - -- ---
10193,7
'
./I
'
'\
'
'
',
\.
__.,__ "__
....:.,.
,'
...
,,
; -- - - - ' -
...............
Fig. C2 Term spiuias ia !he t'OUI'd-SID.te (lslb::!p!) c:onlisuratf011 of c:uWn. All eaergies
are in em-. The 'P. D. :md S terms are spli o u:.
of ekcoron-clcaron repulsion. The
>p tenn is further split with J - 0. I. 2 :as u rcsuh of spin-orbit coupling. The :ie:>k of the
kilter is exagacr.>ted in this Iieure. (From OcKock. R. L.;
H. B.
and Bonding; Bcrtiamin/Cumminas: MC'nlo Park. CA. t980. Reproduced with pcnniuioo.)
s.
The Sl:ltes of carbon are therefore:

D. JP. The JP
further s plit by
differing J values to the terms lP0 l P 1 a nd
T he relative mngnituc.les of
these splittings can be seen in fig. C .2 .
Although the complexity of determining the appropriate
increases with the
number of e lectrons and with higher L values. the method outlined above (known as
Russell-Saunders coupling) may b e applied to atoms with more electrons than the
carbon atom in the foregoing exnmple. S tates for variou s electron configurations are
shown in Table C . I. Russell-Saunders cou pling (also called LS coupling because it
assumes that the individual values of I nnd s couple to form LandS. respectively) is
normally adequate, especially for li&hter Gloms. For heavier a toms with higher nuclear
charges. coupling occu rs between the spin and orbit for each electron. U m I + s}. The
resultant coupling is known asjj coupling. In general. LS coupling is usually assumed
and deviations are discussed in terms of the effects of s pin-crbital interactions (see
Chapters II antl 18).
For alte<oaaivc llf'IJI(IIIChu

lli>cusMon.. see Kircmite. E. M. R. J. Cllrm. EJoc. 19117. 64.
9St-9Sl: lhc inorp.nic twboob lio;lcd on PI> A l and A2, and the references the<ein.
A-12
C Atomie Slain and Term Symbols
Table C.l
T.,.,.. of variaull electroa

canfiguratians
ISl,p, and tfiO

p and's>'
lS
lp -
p2 and p
pl
dandd"
d2 and d
tP and d2
1P,ID, IS
4S,1D, 2f'
2D
d6
tfS
ISIS
ISp
sd
PP
pd
dd
SISS
ssp
spp
spd
Hund's Rules
The ground state of an atom may be chosen by application of Hund's rult!s. Hund's
first rule is that of maximum multiplicity. It slates th:ll the ground state will be that
having the largest value of S, in the case of carbon the lp, Such a system having a
maximum number of parallel spins will be slabiliz.ed by the
energy resulting
from their more favorable spatial discribution compared with thai of paired electrons
(see
principle, Chapter 2).
The second rule states that if two states have the same multiplicity, the one with
the higher value of L will lie lower in eneray. Thus the ID lies lower in energy than the
s.s The greater stability ofstates in which eleccrons are coupled to produce maximum
angular momentum is also related to the spatial distribulion and movemenc of the
eleclrons.
'"'Mnd
' Huad's rules an:

ito p<edictilla the CO<RCt
stale of on 11om. Thc1'C an:
cxa:ptions when the rub are ueed 10 preclict the ordcrina or
stutn.
Appendix
D
Character Tables
Nanoxiol Groups
c,
cl
(Th
.r, y, R<
A'
xl, yz,
z.l,
-I
z.R,.,
R.,
R,, Ry R,
X)l
- I
A.,
)ll.,Xl.
_r2, yl, z.l

xy, xt. )ll.
X , )l,l.
c. Gnlups
Cz
c)
cl
A
8
-I
c.
{:
c)
I I
{:
t"
cxp(2wi13)
z.
x' + y2, z.l
(.r, y)(R, . R1 )
(z2 - y2, .ry){yz, .rd
c. cl c!
xZ, 1z, z.2, xy

yr.xz.
I
-I
x' + y:,
t, R.
I -I
- I
-I - I
-a
(X. y)(RI"
42
xz- yl, xy
R,)
()IZ. xv
D. Groups
Oz
A
81
8,.
B,
C1(tl C,(y)
I
I
- I
- I
I
- I
-I
Ct<xJ
.r2, yz,. zl
-I
-I
I
z, R,
y, R,
X)l
Xl.
.r, Rz
)ll.
D,
2CJ 3C2
AI
I
I
Az
I
- I
- I
0
z., R,
(x,y)(R.. ,
z2 + yl,zl
R)
(.r1
yz, .ry){Xt, YV
A13
l"
Groups
s4
A
8
E
I
I
t:
s.
('l
I
-I
i
I
I
-I
I
-I
-i
s.
l
.tl + yl, z2
... - yl, xy
(.r, yl; (R,. R,l
l.rz, yl)
R:
_, -a
A,
c)
I
I
ft ,.
" I I I
A.,
E.
{: tf t
I
{I
I
I
I
I
-I
-I
- I
sl s.
I
E C1
.,.,.(.rl) cT.(yl)
A,
A,
I
I
- I
-I
I
- I
B,
B,
I
I
I
I
E 2C4
C2
A,
A,
E
I
I
I
I
2
c...
E 2C 2C) C1
B,
B,
A,
A,
B,
B,
Ez
I
I
I
I
2
2
-I
I
I
-I
-I
I
I
I
I
-2
I
-I
-I
I
-I
I
I
I
I
-I
-I
I
-I
-I
I
R,
.r, R7
y, R,
2a.
'J.qJ
I
-I
I
- I
0
I
-1
- I
I
0
I
I
- I
-I
-2
2
c,
E 2Cl 3a.
.rl, y1, zl
xy
A,
A,
Xl
I
I
2
I
I
-I
I
-I
0
cj.
A,
Az
,
,
I
I
2
2
-I
-(
.rl
R,
(.r, y)(R,. R.>
+ ,.,, zl
.rl - yl
xy
(.rz, yz)
3a. 3aJ
I
-I
-I
I
0
0
.rl
.rl
R,
(.r, y)(R,, R.)
exp(2'11'i/3)
.rl + yl,
(.rl - y2, .ry);
(.rz, yl)
-f}
-(
(.f, y)
+ yl,zl
(.rl - yl, xy)(.rz, yz)
Jl
-I
I
-I
0
0
R,
fR,, R1 )
f.
-I
Ca Groups
c,.
l.t, ,YIIR,. R7)
+ y2, zl
(.rz. yl)
(.rl - yl, .ry)
2Cl
2
2
Sa.
cos 72" 2 cos

cos 144" 2 cos
I
-I
144"
0
0
R,
(.r, y)(R,, R1 )
.rl
+ yl,zl
(.rz, yz)
(.rZ- yl, .ry)
D.., Groups
Dv.
A.,
I
I
I
I
I
I
Bl.t
Bl.t
B,.,
A.
B,.
Bz.
C2( y) Cz(.rl
I
I
-I
-I
I
I
- I
- I
I
-I
I
- I
I
-I
I
- I
8,_
E 2C4 C2
A,.,
AIN
I
I
I
I
-I
- I
I
I
I
0
I
I
-I
-I
E.
I
I
I
I
2
-2
D511
2Cs
A'I
A'l
I
I
2
I
I
B,.,
B!.t
A,.
Al
B,.
Bz.
Ej
El
Ai
Ej
rt(.rl)
17( yl)
I
I
-I
-I
-I
-I
I
I
I
-I
I
-I
-I
I
- I
I
I
- I
-I
I
-I
I
I
-I
I
I
I
I
-I
-I
- I
-I
I
-I
-I
I
I
-I
- I
I
2Ci 2C:i
I
I
-I - I
I
- I
-I
I
-2
I
I
I
I
-I
-I
I
-I
-I
I
-I
-I
- I
-I
-2
I
I
I
I
I
I
2 2 cos 72" 2 cos 144"

2 2 cos 144 2 cos n
I
I
I
I
zl, yl, z2
R,
R,
R
X)'
DJJo
E 2C3 3C1
Aj
A'2
I
I
E'
.11:
.)'l
Aj
A.1
E"
2
I
I
I
I
-I
I
I
I
-I
- I
2S, lu.
ult
I
I
I
- I
-I
-I
-2
.)'
.r
lu. 2rr"
2S. lilt
I
I
-I
-I
0
-I
- I
I
I
2 cos n 2 cos 144

n
2 2 cos 144" 2
I
I
u(xy)
I
I
I
I
I I
- I -I
I
-I
.rl- yl
xy
-I
I
-2
-I
-I
- I
- I
l
-I
I
-I
I
-I
I
I
- I
+ yl, :tl
,c!
R,
<R., Ryl
(xt, Y:t)
0 I (.r, y)
sc1
CTit
2S,
I
- I
I
I
I
I
0
0
2 cos n
I
I
2 cos 144"
2 cos 144
2 cos 72"
I
- I
- I
-I
-I
-I
- I
- I
0
0
-2
-2 cos 72"
-2 cos 144"
Srr.
- 2 -2 CO$ 144 -2 COS 7r
I
-I
0
0
xl + yl, zl
R,
(.r: .)')
(.rl - yl, xy)
- I
0
0
lz(R.t R,.l I
(Xl, yl)
I
I
-I
-I
-I
I
-1I
0
-I
I
R
(.r: y)
I (R., R.)
l
.rl
+ yl, zl
(.rl - yl, .ry)

I (.r:t, yd
;:
D,., Groups (Continued)
Dw,
E 2C6 2C3 C2 3C2 3Cl
A,.,
I
I
I
I
A2x
B,.,
Bz,
,.
A,.
Az,
s,.
Bln
2
2
I
I
I
I
--
--
--
,.
Eln
2
2
D&lt
E 2Ca
A,,
I
I
I
I
A2x
Bz,
,1
Ez,
,,
A,.
Alii
B,.,
Blot
e,.
,.,
EJ
2
2
2
I
I
I
I
2
2
2
I
I
I
I -I - I
-I
I -I
- I - I
I
-2
2
I
I
I
I -I - I
I -I
- I
-I - I
I
-2
2
0
0
0
0
2Sl 2S6 crh
I
I
I
I
I -I
I -I
2
I
2 -I
-I -I
-I -I
I
-I
I
-I
-2 -I
- 2
I
I
I
I
I
-I
-I
-I
3crJ 3cr.
I
I
I -I
I -I
-I
-I -I
I
-: I
- 2
2
0
0
-I -I -I
I
-I
I I
- I
I - I
J
-I
I
I -I
I 2 0 0 I
I -2 0 0
-1
1 xl +
y2, zl
R,
(R,, R1 J
(xz, yz)
(.fl - yl, X)')
z
(x, y)
I
I
-I
-I
I
I
-I
-I
Vi - Vi
0
0
- Vi Vi
I
I
-I
-I
I
- I
-I
Vi - Vi
0
0
-Vi Vi
2c.
4C2 4Ci
I
I
I
I
I
I
I
I -I -I
I
I -I
I -I
I
- 2
2
0 -2
0
-2
I
I
I
I
-2
0
0
0
0
0
I
I
I
I -I -I
I
I -I
I
I -I
-2
2
-2
0
0
0
0
2S:
I 2S8
I
I
I
I
2
2
2
-I
-I
-I
-I
-2
-2
-2
I
I
-I
-I
I
I
-I
- I
Vi -Vi
0
0
-Vi Vi
-I
-I
I
I
2S4 crh
I
I
I
I
4crJ
4cr.
_: I
I
I
I
I -I
I
I - I
I - I
I
0 -2
-2
2
0 - 2
0
0
0
0
0
0
2
2 -2
0
2
0
0
0
(R,, R1 J
-I -I -I - I -I
-I -I - I
I
I I
I -I -I -I
I
I - I -I
I -I
- Vi Vi
0
0
Vi - Vi
R.
0
0
0
z
(x, y)
1 xl
yl,zl
(.fz, yz)
(xl - yl, xy)
Cubic Graups
T
I E 4C,
I'
E{A :
T
Th
A.,
A.
E
E.
r..
E
I
I
{:
{:
3
3
TH
t
0
4C3
I
I
I
I
I
- I
xl + 1 : + tl
C2t2 - x2 - .,:.
xl _ yl)
(xy, Xt , yl)
(R: R RJ; (X, y, t)

I
4S6
I
-I
I
I
- I
-I
I
- I
3C2
I
I
t
t
0
0
I
I
I
I
I
I
-I
- I
-3
- 3
A,
I
I
I
I
- I
I
I
I
- I
0
I
-I
- t
f
- -
0
0
E 8C3 3C2(C!I 6C 6C1
A,
Al
I
I
2
3
Tl
I
I
- I
0
0
I
I
2
- I
-I
exp(2,.;13)
I
-I
xz + yz + zZ
I
- I
(2tl - xl - yl,
:J
xz - yl)
-I}
-I
-I
(Rz
Rtl
(X, y, t)
yl
I
-I
- I
I
(.n, yt, xy)
yz, xl
- yZ)
(xy, xt. yl)
.rl
I
-I
tl
(2zl - xl -
(R,, R,, R,)

(x, y,l)
-I
I
exp(2'1ri/31
Jqh
.rl
0
0
I
-I
T,
Tl
0 -I
0 -1
I
- I
"
-(
...
I
t
E 8C, 3C1 6S4 6uJ
r,
"'4
f -
Td
Al
:J"
3C2
yl
zl
(2zl - xl - yl , xl - y1)
(Rz R1 , R,); (x, y, tl
(xy, Xl, yl)
o.
AIN
Az
"
Tllt
A,.
Az.,
E.
r,.
T2
/! IIC) 6C: 6C4 JC2 ("
I
I
I - I
2 -I
0
J
u -I
0
I
3
I
I
I
I
I - I
2 -I
0
0 -I
3
I
3
0
I
I
I -I
I
I
I
I
I
-I
2
u
3
I
3 -I
I
-I
-I
-I
-I
I
-I
6S4 liS,.
-I
I
I
- I
- I -I
0 - I
-I
- I
-3 -I
-3
I
I I ex, y, z>
-I
c.,. Groups
Cv.
A.
I
I
I
s.
A.
B.
c)lo
A'
A"
t::'
c2
O'h
I
I
I
I - I
-I
I -I -I
I
I -I -I
cl
{:
I
{:
I
( .
E" (
E'
E'
l
X,
sl s'
ah
x2, y2, z2, xy

xz. yZ
R,
R R1
.. exp(2?Ti/3)
I
I
I
(
:}
I E'
-I -I -I
-I -_ E
E'}
E' -E
-I
+ yz,
R,
.r2
(.r, y)
(xl -
(R,, R1 )
z2
yz , .eyl
(.rt, Yl)
zl
(2l2 - ,r2 - y2, 2 - yl)
<R.,. R R,l
- I -I
I
- I
I -2
xz + yz
I
I
I -I
-I -I
I
-I
-2
-I
6.rJ
(xz. yz, .ry)
c. cl
I
I
A6
8.
.
{:
AH
8
E
I
-I
I
-I
I
- I
I
-i
I
I
{:
I
I
-I
-I
I
I
-I
- I
-I
I
I
I
-I
-I
I
I
-I
- I
s.
s!
-I
-I
I
I
- I
-I
- I
-I
I
I
I
-I
I
-I
-I
I
-i
- I
,cl + yl, ll
xl - yl, XY
R,
I
- I
-a
R1 )
-I
I
_;}
(Xl, )Ill
(X, )I)
D.d Groups
Du
A,
At
R,
81
E
t:
2.S.
I
I
I
I
I
I
-I
-I
c,
2Cl 2trJ
I
I
I
I
-I
I
I
- I
-I
I - I
-2
0
2C1 3C1
DJJ
xl
R,
I
I
xl _ yt
:ty
l
(f. ,1'):
+ yl,ll
c.u, Yl)
IR,. H. l
t:M
A,.
I
I
A1
EH
D'"'
lSa
A,
At
8,
I
I
I
I
81
1
)
>0
2
2
2
2C4
I
I
-I
- I
v'2
0
-v'2
I
I
I
1
0
-2
0
2s: c,
I
I
- I
-I
-Vi
0
v'2
I
I
-I
I
I
- I
4Ci 4uJ
I
I
I
I
-2
2
-2
I
-I
I
- I
0
u
0
I
-I
-I
I
0
0
0
1 xl + yt, :l
R.
l
(.f, y)
(R,, R,l
(xl -
y1, xy>
lxt, Yll
2S 6 3uJ
I
- I
I
I
I
- I
-I
-I
-2
I
I
-I
- I
-I
I
I
- I
0
-I
I
,cl
+ yl,
zl
R,
(R,, R1 l
I (x,
l
y)
(,cl - yl , XyJ,
yd
(,n,
A-20
DCha racter Tablea
Du
A,,
I
I
2
2
I
I
2
2
Ab
,,
Et.
A,.
At.
b
D6J
2C5
I
2 COlO 7r 2 cos 144"
2 cos 144" 2 cos 72"
I
I
E 2S,l
zs.
- I
2 cos 72'"
2 cos 144"
2 cos 144"
2 cos 7'!'
0
0
-I
zs:2
2C,
- I
cl
(,q<l
I
- I
- I
- I
- I
B:
,
,
;
.
2
2
2
2
2
0 -2
- I - I
- vl
2
0
2 - I
0
- I
6Ci
I
I - I
I
- I
I
I - I
I
- I
I - I
y'j
I
0
0 -I - vl - 2
2
0
I - I -2 - I
I
B,
_,
0 - 2 -2 cos 72" - 2 cos 144"

0 - 2 - 2 cos 144" - 2 cos 7r
A,
Az
2C6
I
- I
- I - I
2 cos n 2 cos 144"

2 cos 144" 2 cos 72"
Scr<l
xl
0
2
0
2
I - I
I
I
- I
2S,o
- 2
- I
2
y'j - 2
-I
0
0
<R
R,)
(x, y)
0
0
x> + yt, t l
t
(x. y)
t.f2 - yl, .ry)
0
0
0
(R,. R,)
(.a, yt)
c_ ...c1 o.,.
c_
A 1e!
Az!1!"
1en
;..
-.. ..
n,
""<T,
I
I
-I
2
2
2
.1J.
2cos
2 cos
2 cos
(x. y); (R,, R,)
(.a. yt)
t,t2 - yl. xy)
0
2S!
""<T,
coC2
xl
- I
2
2
2 CO$. 
IJ.,
2 cos
0
0
!;
I
I
I
I
-I
ll..,
2
2
n..
xl + yt. zl
z
R,
2
2 cos
I
0
- I
:! - 2
2c:os
-I
- I
- I
-2
- 2
_,
0
0
- I
tl
R.
CR,. R,l
t
0
0
+ yz.
(x.y)
(Xt,yd
t.fl - yl. xy)
R,
- I
I
+ yl. z.2
R.
(xz. yz)
(,C: - yl, X)')
Append
E
Bond Energies and Bond Lengths
Alll'lougJl the concept of bond energy seems intuitively simple, it is actually rathe
complicated when inspected closely. Consider a diatomic molecule A-B dissociating. lt might be thought that it would be a relatively simple matter to measure ll'le
energy necessary to rupture the A- B bond and get ll1e bond energy. Unfortunately,
even if the experiment is feasible the result is p:nerally not directly interpretable in
terms of "bond energies" will'lout further wort.
the factors to be considered
are the vibrational. rotational, and translational eneraies of the reactants and products.
the zero-point energy. and pressure-volume work il' enthalpies are involved. The
interested reader is referred to books on thermodynamics for a complete discussion
(especially Dasent, W. E. Inorganic Enugetics; Penguin: Harmondswol1h, Enstand,
1970). The following is meant as a brief outline of the problem.
Consider the energy of a diatomic molecule as shown in the figure. The concept of
bond energy may be equated with the difference between ll'le bollom of the energy
curve and the energy of the completely separated atoms
However. as a result
of the zero-point vibrational energy of the AB molecule. even at 0 K. the energy
necessary to separate the atoms AU is somewhat less (by a quantity of lhl. The zeropoint energy is greatest in molecules containing ll11ht utoms such as hydrogen (25.9 kJ
mol- 1; 6.2 kcal mol- 1 in H2 ) and oomewhat
in molecules containin11 heavier
atoms.
There is a corresponding difference between two estimates of the bond distance in
a molecule A-B. One. ' corresponds to t he minimum in the energy distance curve
(see figure). The second. r00 corresponds to ll'le average distance in a molecule
vibrating with zero-point energy. Since the curve is not perfectly parabolic ll'le two
values are not identical.
If ll'le dissociation is to take place at some temperature, T, other ll'lan 0 K, the
energy necessary to accomplish the dissociation must include an amount sufficient to
provide ll'le separated atoms with the translational energy at that temperature
Compensating in pan for this will be the translational. rotational , and vibrational
energy oflhe molecule AB at temperature T(-6.3 kJ mol - 1; - I.S kcal mot- for H2 at
298 K). The difference between the dissociation energy at 298 K
and ll'lat at 0
1; -1 kcal
K (AUo) is very small (-I kJ
for H2).
<iRn.
mor
mort
A-21
A-22
E Bond Enervin and loncllangths
The quantity which is generally more accessible experimentally is the enthalpy.

The enthalpy of dissociation at a given tempemaure differs from the energy of dissociation by Pl1Y wortc: -2.S JcJ mol- 1; - 600 cal mot- at room tempemlure. Some
examples of the various quantities fOt" H 1 are:
H1
-------
l1Ud
l1U0
llUm
l!Jfm
2H 458.1 (109.5) 432.00 (103.25) 433.21 (103..54) 435.93 (104. 19)
Since the last three values-those most often quoted for ''bond energies"-ditrer by
very lillie, the difference may be ignored except in precise work.
The electronic energy, l1Ud, is of interest mainly in connection with bondill8
theory since it is not an experimentally accessible quantity. A second quantity of this
type is the "intrinsic bond energy," Ihe difference in energy between the atoms in the
molecule and the separated atoms in the
stale. i.e., with all of the atoms in the
same condition (with respect to spin nod hybridi:zation) as in the molecule. lt is a
measure of the strength of the bond after all other factors except the brinaing together
of valence stale atoms have been eliminated (cf. the discussion of methane. Chapter 5
ond McWeeny, R. Coulsnn's Yaltnce, J rd ed.; Oxford University: Oxford, 1979;
Chapter 7).
The situation becomes further complicated in polyatomic molecules. The energy
of interest to chemists, generally. is that associated with breaking the bond without
any change in the remaining parts of the mulecule. For example, if we are interested in
the bond energies in CH 4 Of" CF4 , we wish to know the energy of the reaction:
X
x/1'-x
X
-------
x/1'-x
+X
In general, the qua.sitetrahedlal species CX3 is not observed. In CF3 a pyramidal

molecule approaching this configuration is found. but in CH3 the resulting species is
EBond Energies and Bond Lengths
A-13
planar with sp2 hybridization instead of spl. The energies associated with various
dissociative steps for methane are:
mor- (101.6 kcal mol- 1)
CH4 --+ CH3 + H
l!.U = 421.1 kJ
CH) --+ CH2 + H
l!.U = 469.9 kJ mot- (112.3 kcal mol- 1)
CH2
---+
CH + H
CH --+C+H
l!.U =- 41S kJ mol- 1 (99.3 kcal mol- 1)

l!.U = 334.7 kJ mol- 1 (80.0 kcal mol-
We can associate the greater energy of the second dissociation step with a presumed
greater bonding strength of trigonal: sp! hybrids over sp' hybrids. Whether we
understand (or at least believe we do) the reasons for each of the quantities listed
above or not, it is obvious that
represents the bond energy in methane. However,
since the summation of these four experimentally observable proce.sses must be
identical to the energy for the nonobservable (but desirable) reaction:
CH4
--+
C + 4H
theaverageofthese four quantities (411 kJ mol-1 ;98.3 kcal mol- 1)can be taken as the
mean bond
for the C-H bond in methane.
The mean bond energy is a useful quantity. but it should be remembered that it is
derived from a particular molecule and may not be exaclly correct in application to
another molecule. Thus if the total bond energy in dichloromethane does not equal
awo times the average bond energy in methane plus two times the avel'll8e bond energy
in carbon tetrachloride, we should not be surprised. The presence ofbomls of one type
may have an effect in strengthening or weakening bonds of another type. As a matter
of fact, there is no unequivocal way of assigning bond energies for molecules such as
dichloromelhane by means of thermodynamics . The summation of all of the bond
energies may be determined as above for methane, but the assignment to individual
bonds must be made by secondary assumptions. e.g . the bond C-H energies are
comparable to those in methane. Alternutively. the bond energies in molecules containing more than one type of bOnd may be assigned on the basis of some other type of
information such as infrared stretching frequencies.
One of the most serious problems hindering the assignment of bond energies
arises for bonds such as N-N and 0-0. The nitrogen triple bond and oxygen
double bond may be evaluated directly from the dissociation of the gaseous N2 and Oz
molecules. Single bonds for these elements present special problems because additional elements are always present. For example, consider the following dissociation
energies accompanying splitting of the N-N bond:
N2 H 4 - - + 2NH 2
D0 = 247 k1 mor 1 (S9 kcal mor 1)
N 2F4 - - + 2NF2
D0 = 88 kJ mol- 1 (21 kcal mol- 1)
N2 0 4 - - + 2N01
D0 = S7.3 kJ mor1 (13.7 kcal
rnor 1)
A-24
EBond &orgies and Bond long1h1
None of these represents the breaking of a hypothetical, isolated N-N bond:
By using N- Hand N-F bond energies from NH3 and NF3 it is possible to estimate
lhe inherent strength of the N-N bond:
Tolal energy of atomization, N 2H 4
4N-H bonds (assumed from NH.J
Difference (equated with N-N)
Total energy of atomization, N2 F4
4N-F bonds (assumed from NF.,)
Difference (equated with N-N)
1703 kJ mol- 1 (407 kcal mol- 1)

1.544 kJ mor (369 kcal mol- 1)
1.59 kJ mol I (38 kcal.mol- 1)
1305 kJ moe (312 kcal moi- 1)
1134 kJ mol- 1 (271 kcal mol- 1)
172 kJ mol- 1 (41 kcal mol- 1)
The results of this calculation are gratifyingly congruent, and we feel reasonably
confident in a value of about 167 kJ mol- 1 (40 kcal mol- 1) for the N-N bond. Similar
results can be obtained for hydrogen peroxide and dioxygen difluoride 10 obtain an
estimate of about 142 kJ moe (34 kcal mor 1) for the 0-0 bond.
Although the calculations for N - N and 0-0 bonds are self-consistent, there is
always lhe possibility that a wider series of compounds would show greater variability. This is especially probable in molecules in which the electronegativity of the
substituents is believed to affect the bonding by particular orbitals, e.g., overlap by
diffuse J orbitals. Thus on lhe basis of observed stabilities the presence of electronegative substituents such as -F and -CF3 seems to stabilize the P-P bond
relative to H2P-PH 2 , although there are not enough data to investigate this possibility quantitatively.
There is at present no convenient, self-consistent source of all bond energies. The
standard worlc is Cottrell. T. L . T1u! Strengths of Chemical Bonds, 2nd ed.; Buuerwonhs: London, 1958. but it suffers from a lack of recent data. Darwent (National
Bureau of Standards publication
31, 1970) has summarized recent data
on dissociation energies but did not include some earlier work or values known ooly
for total energies of alomizalion rather than for stepwise dissociation. Three useful
references of the Iauer type are: Brewer, L.; Brackeu, E. Chem. Rev. 1!161, 61, 425;
Brewer, L.: er al. Chem. Rev. 1963, 63, Ill; Feber, R. C . Los Alamos Repon
LA-3164, 1965. The book by Druwent mentioned above also lists bond energy values
for some common bonds.
Table E. l has been compiled from the above sources. The ordering is as follows:
hydrogen. Group lA (I), Group IIA (2), Group IIIB (3), transition elements, Group
lilA ( 13). Group IVA (14). Group VA {IS), Group VIA (16), Group VIlA (18). Group
VIllA ( 19). For a given group (such as lA I) the compounds are listed in the following
order: halides, chnlcogenides, etc. Unless specified otherwise. the bond energies are
for compounds representing group number oxidation states, such as BCI3 , SiF4 , and
SF6 Other compounds an: listed in parentheses, such as(TICI) and (PCI.,). Values are
for the dissociation energies of molecules A-B and mean dissociation values for
ABn. For molecules such as N2 H4 two values are given: H1 N-NH2 represents the
dissoc;ation energy to two amino radicals, and N-N (N1 HJ represents lhe estimated
N-N bood energy in hydrazine obtained by means of assumed N-H bond energies
as shown above.
E Bond Energies and Bond lengths
Tobie E.l
Bond energies and bond

langths
A-25
A-26
Elond Ene rgi and Bond Lengths
Table E. I
r
pm
226.6
278.7
294.5
317.7
2.266
2.787
2.945
3.177
234.5
29D.6
3()7.2
JJ/.5
2.34S
2.906
J .(J72
3.315
140
175
191
210
JJ3.1
/ .40
1.75
1.91
2.10
1.331
177
218
234
254
174.9
1.77
2.18
2.34
2.54
1.749
2.10
2.51
0
2.67
2.88
1.822
E lond Enervies ond Bond lengths
A-27
Table E.1
[Cotrtittued)
Y-Y '
Y-F .
Y-0 '
- 11
37.3
-uo
:i: s
- 118 '
- IOJ
86.7
57.6 :t
Y-Br
l
Y-1
t
La-La
La-F
La-GI ,
1
La-Br
'
La-1 -
-m
lI
,,
ll2.6
- f()j
86.9
l.cmtl.cmides and cxtimcles 11<J -r'I

M.tal
Me,
Mlr,
MF:o
Ml
-644
-J$6
499.6
-431
Ce
]33.$
-62]
Pr
481.4
-418
]2].8
Nd
-170.7
-406
-J8j
-$90
Pm
-4$2
- JOS
- 285
-565
-m
Sm
-360
-Jj2
:..w
- 272
-414
Eu
-:U3
-619
-48$
- 418
Gd
-3]9
-410
Tb
Dy
-577
-377
- JOS
-444
- J05
Ho
-$77
-381
-444
- 310
-582
-448
-331
Er
.-548 -418 _..;...:::3$1 _ _ ::-2$1
Tm
- 251
-519
-385
-321
Yb
-]43
-410
Lu
-607
-;
Th
Pa
-]4J
424.J
-619
495.4
u
- ]26
Np
-$86
--460
-397 ...
- JIO
Pu
561.7
442.2
378.7
-4$2
- 318
-573
- 389
'*s
'*
'* .
- --&.
-m
-m
Ce
'*
-154
_J
__
-<
Metal
rr;..-
I
U/.0
598.0
-$61
-SJ6
$22.2
561.8
-519
- 485
-m
M#s
'*
-4Z7
-519
\
-!
E Bond Enrgies and Bond Lengths
.
Mls
..
, -SIS
,.
'
101.4
-60
"
' Mf.
Mfs
MF6
t.
'J
153.2
143.0
-134
-128
-124
/35.0
-124
- 116
124.8
-114 '
-/02
J.
E Bond Energies ond Bond t..ngrhs
A29
{Con,;,-i)
2.25
75:1: 5
69 :1: 10
61 .4
, 254.4
-7J
.i
2.544 .
. fo..
!'
69 :1: 15
--6()
p.';
181
1.81
2.29
'2.41
70..:1:
.. ;!
..
146.'5 :1: 13
":;
109
90
175
1.75
A-30
E- Bond EnHgtel ond Bond Lengths
Table E.l
Bond
ln-Br11nBr)
fn,.-l(lnl) .
.-'f'
TI-F(TIF)
TI-O(TICI) -:->
n-BiiTIBr)
TI-I(TIO
A
2.543
2..754
2..485
2..814
A31
E Bond EnHlliH a...! lo11d leng1hs
Table E.l
{Conlinuecf)
De
lccal
Sn::_BJiSnBrJ
Sn-Br(SnBr,)
So-I(SniJ Sn-I(Snlz>
Pb-F(PbFJ
Pb-F(PbF2)
Pb-Br(PbBrJ
Pb-Br(PbBrz)
Pb-I(PbiJ
Pb-l(Pbl2)
65.2
329.3
78.7
- 105
61.5
U9
r13
;.: "l
242
2.41
2.69
1.73
- 79
94.1
-58
-243
246
255
-49
16/,j
-331
394.1
Pb-O(PbCIJ
Pb-ci(PbCI2 )
pm
272.8
303.8
72.6
-101
260.2
- 142
-48
61.2
-34
49.0
205.0
2.79
GrOp VA (15}
- 40
- 167
S9 ::1:: 3
HzN-NH1
14S
115
109.8
100
225.07 ::1:: .II
68 ::1:: '
N-F
136
17S
N-Cl
N-Q
N=O
48
140
145
Ill
NN
162
liS
Ul
4ll
P-P(PJ
57
OzP-PCiz
liS
P=!P
::t:
P-CI(PCI,J
63
44
P-0
80?
- 130
- 80
lS
91 ::1::
P=O
P=S
As-As(AsJ
As2:1As
As-F(AsF,)
- ISO
186
243
-l.S
1.86
1.43
- 97
115.7
76.9
61.7
47.8
12 .
-:;-93
189.3
1.893 . i
.. ,54 - - 1.54 --4
203
2.03
I
117
78
-- - - -
1.45
1.15
1.098
1.36
1.7S
1.40
1.11
l.lS
2.11
.tt.
'l
,
;_.
171.1
116.1
133
254
i::
178
.{
A-32
Ene rgin and Bond Lengths
Tobie E.l
o.
kcal mol- 1. ,
Bond
Bi .... Bi
Bi-F(BiF,)
Bi-F(BiP1)
Bi-CI(BiCI1)
Bi-Br(BIBr1)
191 :1: 4
....;.297
..:393
168.2
- 142
HO-OH
207.1
:1: 2.1
493.59 :1: 0.4
0=-0
O- F
189.S
226
S-S(s_)
us :1:
21
4U.7 :1: 6.3
s-s
S-F
S-Cl(Sz<lz>
S-Br1SzBrz)
284
25S
2177
s11.1 :1: a
532.2 :1: 8
468.8 8
172
272
S=<>(SO:z)
Se-Se(SeJ
Se=Se
Se-F{SeFJ
Se-F{SeFJ
Se-F(SeF2 )
Se-0(SeCI4 )
Se- CI(SeCI 2)
Se-Br(SeBr.J
Se-Br(SeBrz)
Se-I(Sey
Te- Te
Te=Te
Te-F(TeFJ
Te-F(TeP.J
Te-F('feF2) .
Te- O(Te04)
Te-BrtreBr4 )
,.
284.9
-310
-351 - -- 192
- 151
-201
- lSI
(126)o
218 :1: 8
329.7
-335
:1:
1 't'
- 94
274.5
Group VIA (16)
46
-71
65.6
55.5
40.2
- J.4
49.5 :1: 0.5 ,,
117.117 :1: u .
148
I 1:48
120.7
'1:207
205
1118..7 ,
i os
--t< 142 .. ... 1A2

-,
45.3
S4
2.05 ....
<
64 :1: s
101.5 :1: 1.5 tl
1.,
68
1.887
'\ 1.56
t , 'JJY1
. 2.07
"
227
. 2.27
w.6 2 , 149.3 '"'
1.493
127.2 :1: 1 .1. 143.2
; 1.432
4
112.1 1
143 '
L43 ,
41
-.
_ 1i
11 <.
6S 115.2
-!" ' 2.152
61
. S2?
68.1
---74'-IU
- .s&
- 36
- -43
-36
71J.8
.:;
'
t
'1
"
..,
"' ..-,.
1.
,; -
"
-:
'
' }
r1
'
-A
(30)"
52 :1: 2
-80
-;
. :
r:
r
,;
r . J,
l' .:'
a::. . .;
f-,+
r .,.J
...
<=" '
11
.. ,
E lone! EMrgieo one! load Lenglhs
A-33
Table E.l
Do
kJ.....rl
Br:._Br;
\.":.
-Br;r-F(BrF:J
'B r,-F!BrF)
Br:...0{BrCO
;r
Br-()(Br-OH) !
'Cr-:-<:1 ".
'
CI!...F(CIF,)
CI.-F(QF,)
CI-F(CIF)
0-0(CI-()H)
.F-F ,
-f>t-At ,
190.16 :1: 0.04

187.06
201.2-b
249.4
215.9:1:0.4
201
2YJ.1 :1: 0.4
- 142
172.40
248.9 :1: 2.1
2 18
154.8 :1: 4
115.9
lcml moa-
.,
r
P"'
228.4
A
2.284
.172,J84d
175.6
213.8
1.72.1.84
1.756
2.138
1.98.8
1.988
169.8
162.8
1.698
37.8 :1: 1.0

'1:7.7
141.8
1.418
1.90'
1.95'
45.45 :1: 0.01

44.7
48.1
S9.6b
51.6:1:0.1
48
57.3:1:0.1
-w
41.2
59.5 :1:
o.s
1.628
52
Group VIllA (18)
i
Xe-F(XeFJ
Xe-F(XeF2)
ZXe-o{XeO,) .
;Kt':;....'r{KJ:F:z) "
r .,
l30.4130.8-
30.2'
190'
31.2'
19S
31.3
:zo.
2IJ()r
8-V
50-
12
175'
190'
Huheey: J . E.; Evans, R. S. J.
z.oo1.75'
1.9-
r_,. Nflrl. Cltmf. IP'It, J1. lll.
t"''
t;
Sla..:
CMmisrry
l33.
'c- Hanhberaer W.; ct II. J . Am. Cltmr. Soc. 1967,69, 6466.
;,
o7;
f . N., Jr. J. CMm. Pl!y1. 1957, n. 982.
J. H_. NDIM-Gtu ChtmU/TJ: Mtthuen: Loadan, t968.
Values in boldface type are from Darwem and represent his estirnales of the .. best
value .. and uncenaimies for the energies required to break the bonds at 0 K. Where
values are not available from Darwent. they nre taken from Brewer and coworkers for
mellll halides and dihnlides
italics) or from Feber for
metal.
lanthanide. and actinide halides (italics). These values represent enthalpies of atomization at 298 K. The remaining vakles are from Courell
numerals) and other
sources
with superscripts keyed to references at end of table).
The table is intended for quick reference for reasonnbly accurate values for rougJl
calculations. No effon h:IS been made to conven the values from 298 K to 0 K. and in
many cases the errors in the estimates are grealer than the correction term anyway.
The accuracy of the values can be llfllded in :1 descend ina scale: ( l) those giving :!: uncertainties; (2) those giving "exact" values to the neatest 0. 1 or l ; (3) those expressed
as ..about" a certllin value(- ); and (41 those which nre almost pure
followed
by a question mark. AU values are experimen!DI except for a few for which A-A
bond energies are not known but would be helpful (as for electronegativity C:llculations). Estimates for these hypothetical bonds (such as Be- Be) are listed in parentheses.
The bond lenglhs nre mainly from two sources: Tablts of lntt'raromic Disruncts
and Co'lfigurotion in Molecults and Ions (The Chemical Society. Special Publication
No. II. 19.58) :llld Supplement (Special PubliC:ltion No. 18. 196S) with values given in
boldface, and Brewer and coworkers (italics). A$ in the case of the energies the
purpose of the table is for quick reference Md the bond length is given liS a typical
value that should be accurate for most purposes :t: 2 pm (0.02 A).
For special purposes and precise computations, the oriainal sources should be
consulted for the value, nature, and source of the bond energies, Md for the accuracy.
experimental method. and variability of the bond lengths. Space requirements prohibit
extensive tabulation of information of this type here.
F
An Overview of Standard Reduction
Potentials of the Elements
T he following table gives a quick ove,r view and perspective of electrochemical potentials of the elements. For each group of elements, br.lc:kets indicate the limiting
potentials for half-reactions [Mn + ne- - M (metals):
+ ne- - 2XJ..ct(halogens)) of the elements [e.g., u/Li and Na/Na for Group fA (I)) for that group.
Otha- selec:led half-reactions are also listed. Bold-faa: type in the table indicates
important limiting polentials for aqueous solutions (see Olapter 10) and italic rypr
indicates half-reactions in I M OH- . Many elements and oxidation states are omiued
here for simplicity's sake. More extensive data may be found in the d iscussions of the
descriptive chemistry of the elements In the text on the p:JiCS d ted. Potentials in
parentheses are t:slimated values.
TobleF.t
.....
-J.608
' AU p<Untials are stondard udtJctro,r pottllflo/s with ell spec:iu "' unit aaivily ond fucxkY CJ:q>t
for diose V111uesbbelc:d "pH
whichha..:allspeciu unltactivkyexcepl (H,O+} a (OH-)
t.005 x to-.
A-35
A-36
F Azt Overview of Standard Reduction Potentials of the El-ents
labia F.l (c-tinu.d)
Re4ucti<>" tJ/ WDUr ;,.

basic soluJiOtt.
f'nt cn.nailion aeries except Cu t +2- ot.
See pp 58()-$37, $94-599.
Reductloa of neutral water
Reduc:Cion ol ...eer (}flO+)

In Kldk solutloo.
Re4ucJitm tJ/ (<>ridmi<Jn
"'} 0 1 ill basU solution;

tloe revuu is tloe <>ri44-
tioll (dulnlction} of
Gs S<Jlunl.
'
F All
o...niew of Standard Reduction Pat...tial of the Elements
A -37
'1
MnO;
+ H'" +
e- -+ HMnO;
+ e- --+ Ag .
+ zn o + e--+ Mn01 + 40/r

1
NO) + 4HJO + 3e--+ NO + 6H 20
fl(z + 2eBr-
- z
+0.90
---+0.79931
+0.93
o.9Ss
+k078
+ 1.229 .
Mn01 + 4 H)o + 2e-- Mrr+ + 2H20

OJ+ Hp +
-+01 + 201r
+ 1411,0+ + 6e- -+ zc,J + 7H20
+2e--20Ali,. + 2e---+ Au+
MnO; + SH.O+ + Se--+ Mr1+ + 12H10
Mnl+ + e---+ Mn2
Au++ e- --+Au
MnO; + 4HJ0+ + Je--+
+ 2H 20
H 20; + 2HJO+ + 2e- -+ 4H:O
At! + e--+Ag+
a.
+ 2e--+ Rn
o, + zH)o + 2e- -+02 + JH20
XeOJ + 6Hlo + 6e---+ Xe + 6H20
HMnO; + 3H+ + 2e--+ MnOz + 2H:O
H.tXeO, + 2H'" + 2e--+ XeO, + 3H 10
KrOJ + 6Hp + 6e--+ Kr + 6H20
Rn2
F2 + HJO+ + 2e---+ 2HF + 2H20

20F2 + 2e- -+Oz + 2F:
20F2 + Hlo+ + 2e- -+ 0 2 + 2HF
+ 1.23.:..j
.Nil
+
+ I1.36
+ 1.360 .
(+ 1.41)
+ 1.507
+ 1.56
.+1.69 :
+ 1.692
+1.763 .
+ 1.989
(+2.0).
+2.075
+2.10
+2.09
+2.38
(+2.4)
-+7.8901
+3.07
+3.107 1
+3.294
Appendix
G
Tanabe-Sugano Diagrams
[Originally from Tanabe, Y. ; Sugano, S. J . Phys. Soc. (Japan) 1954, 7.53, 766, these
figures are from Figgis, B. N. Introduction to Ligand Fields; Wiley: New York. 1966.
Reproduced by pennission of John Wiley and Sons, Inc. An e xtensive sec of diagrams
of !his son may be found in KOnig, E.; Kremer. S. Ligand Field Diagrams; Plenum:
New York. J9n.)
d 1 , C/84.42
A-38
ao .------,,----,.-T"T"-...,
'A,
801
70
I I I lA"
60
.,
so
40
ill
lo,j
"'c
30
20
10
'SI
I .. "I
:11
()q/8
d'. C/8 4.50

801
10
'Al6
i._
rl' . C/11 4.6
"' ''
; ; ; -- 1
r,
1 -Ttl-11./l lt
r.,,
r.,
t- <F A I
'!""""=
' .
Ml1r
>
;;;
"'
Jr.,
...
d 1, C/8 4.48
:w
'!'
I '.-1 11
()qfB
0.,18
d'
d', C/8 4.6J
IJ<tlll
<1 1, C/8 4.71
l'r,.
App ttnd
H
Models, Stereochemistry,
and the Use of Stereopsis
Paper Models
It is convenient for many purposes to have models available for inspection in order to
realize fully the three-dimensional aspect of molecular and lattice structures. " Balland-stick" models ofvarious stages of sophistication are useful when it is necessary to
be able to see through the st.ructure under considerotion. Space-filling models of atoms
with both covalent and van der Waals radii are particularly helpful when steric effects
are important. The space-filling models and the more sophisticated stick models tend
to be rother expensive, but there are several inexpensive modifications of the " balland-slick" type available. It is extremely useful to have such a set at hand when
considering molecular structures.
Simple tetrahedral or octahedrol models are useful in connection with basic
structural quesl.ions (as, for example, the first time you try to convince yourself that
the two enantiomers of CHFOBr o r of [Co(en),l +l are really noosuperimposable). If
stick models are not available, s uch simple models can be constructed in a few
minutes from paper. In addition. models having bond angles not normally found in
ball-and-stick kits-for example. the icosahedrol borones and carborones-can also
be readily constructed from paper. Paper models are especially useful when large
numbers of models are necessary as, fo r example, in constructing models of the isoand heteropolyanions.
On the following pages generoli7.ed outlines are given fo r the construction of
tetrahedro, octahedro, icosahedro (Fig. H. I) and pentagonal dodecahedro (Fig. H.2).
These outlines may be reproduced as many times as desired by means of photocopying machines. Instructions for cutting are as fo llows:
I. Tetrahedral models. Cut ou t the four triangles enclosed by the TJ brackets
(Fig. H.l) and marked with the venicallines in the drowing. Glue or tape labs
onto adjacent faces to form the tetrahedron.
A-40
2. Octahedral models. Cut out the two sets of eight triangles enclosed by the Oh
brackets and marked with the hori7.ontal lines in the drowing. Glue or tape labs
onto adjacent faces to form the octahedron.
HModela, Ste...,o:hemlatry, o11d lhe Uae of Stereopsla
_.
.,......
..........I
I
.,...-""
II
I
I
'
I
I
'
,. ',J
.......;
........
Rg. H.l
.......
....
A 41
A-42
H Model a,
st..eochemiatry, o...S lhe Uae ol Stereopaia
Fig. H.2
Fig. H.3
HModels, Stereoch..,istry, oowl II> Use of Stereopsis
A-43
3. Chiro/ (DJ) "octoht!dro/'" models. By cutting and pasting in such a way as to

leave "chelate rings on the modell both t:. and 1\ enantiomers can readily be
constructed. Note that having chelate rings on both triangle 2 nnd trillJ181e 7 is
redundant . One may be removed or used as a construction flap. If A = B, the
model has 0 3 symmetry; if A
B. the symmetry is C 3
4. Icosolledral models. Cut out the entire figure drawn with solid lines. Omit the
faces marked "01, only. Construction is facilitated by bending nnd gluing the
two end sections into the "capping" and " foundation" pentagonal pyramids
first. Then the remaining "equatorial" band of ten faces can be wound around
and fastened to these " end groups. The complete icosahedron represents the
B 12Hii" ion or dicurhaclosododecaboranes. Other polyhedrdl boranes can be
formed by removal of the appropriate fuees from the complete icosahedron .
.S. P<!ntllgtJnul tlml<!calrt:drul motlt!l.r. This model cnn be constructed in a similar

way by copying. culling, nnd gluing the pentngonul drawing.
A similar outline drawing for the construction of buckmirluerfuUerene has been
published .l Several other polyhedral models constructed from simple materials have
been descn'bed in a series of articles)
I Noce thai 1his m<:llkl h:&s been

somewhat from Jhe
of Fig. H. l. In previous
edili<n; an :Uiempl """' mode 10 uvoid SlJCh dulnacs btn with lhe awil:>bilily of pholocopyi111
mucbincs wilh sizcalteringo.dju..cmcnts un<llhe Mudcnl's ub;quicous usc oflhem. we have been les$
r=llic1ive in Jhill
oll'erina lhc s1udcn1 11eolcr ftcaitilicy.
2 V1118l. J. D. J. Clrrm. EJuc. 1919, 66. 282.
l Y"""""'. S. J. Cltrm. Educ. 19118, 6$, 10'12
pyr;uni<l); 1989, 66, 1019 (lria"''JJu
dodecahedron); 1990. 61,
t030 (inJctpcncuatifta tfiaonal pyr.unicll. These :m buJ 1hrce examples. Addition:ll oncs11111y be: fuuncl from 1hc references in 11tcsc or by consulti"ll the author indues
ollhc J04li7Wl of Cltrmk<J/ Ed11a11lon between lhc )'CAn 19'19 ond present.
A44
H Models, Stereochemistry, and the UH of Stereopsis
Stereoviews and Stereopsis

Oosely related to the use of models is the corresponding one of stereoviews to
illustrate molecular perspective. The increased availability of molecular data and the
use of computers to genuate stereoviews has made their use routine in journal
accounts of structure determinations. Unlike models, no mauer how useful, stereoviews have the ability to capture the depth of a three-dimensional structure on a twodimensional sheet of pap. An increased number of stereoviews has been included in
this edition.
II is not necessary to view stereoviews three dimensionally: Either half conveys
much information by itself. But every effort should be made to learn the "tricks" of
stereopsis-the amount of insight to be gained is more than rewarding. And although
initial attempts may be fiustrating, it is well worth the effort and the process becomes
increasingly simple and routine. Furthermore, in addition to being a purely informa
tiona! routine. it is an aesthetic experience. Don't be afraid to experiment-each
person has different ways of facilitating the process. However, the following generalizations should be helpful.
The basic principle ("secret"?) of stereopsis is that one is having the eyes do
something that they would never otherwise cJo; that is, each ('Je must louk at a
different image (as opposed to the same image from a slightly different angle). The
common frustration in attempting to look at stereoviews is that first both eyes look at
the left image. then both eyes look at the right image, then both eyes. . . II was to
break this coordinated bebaviot'ofthe human visual system that the old-fashioned and
bulky stereoscope was invented. Today. folding viewers can readily do the job (see
below). By all means. use such a viewer in your initial attempts. II isolates the eyes
from each other. Start with a simple stereoview with Jo(s of visual clues to aid the
perspective; the cubic crystal systems of Chapter 4 are good. Have the image to be
viewed lying perfectly flat. Put the stereoviewer over the images and try to have
everything "squared away." Relax and view the image. You should see a single image
with deplh of field.
Once the above has been achieved, it is usually possible for the (human) viewer to
become sufficiemly adept at the process that the (optical) viewer can be dispensed
with . The "Irick" is to have the eyes looking parallel so that the left eye is looking at
the left image. and the right eye at the right image. The way to have the eyes looking
with parallel lines of sight is to view something "at infinity." It does not have to be the
Andromeda Nebula; across the room will do. Looking over the top edge of the book or
journal containing the stereoview, gaze across the room. Relax. Without making any
particular effort to focus on anything, let your gaze drop to the stereoview. If
successful. you will see three images. The center one is the important one and the one
with stereopsis. The other two are unimportant, except as possible distractions-they
are the left and right images seen "oot of the corner" of the opposite eye. If both eyes
"lock" on to one or the other of the images, look up, rdax, and try again. Try at a
different time ofday, with a different figure, when yoo're fresher, or even when you're
tired. but relaxed.
A third method of stereopsis with which your authors have not been particularly
comfortable. but which many people use quite routinely is the "cross-eyed method.''
Graham. D. M. J .
Educ. 1986. 6J, 8n.
H Moclels, St-odtemistry, a!ICI the UM of St.reopsis
A-45
Quite simply, it is just that: The lines of sight of the eyes are crossed and the right eye
looks a t the left image and vice versa. The method works because most people have a
greater ability to command their eyes to cross lhnn to commllnd tlrrm to rrmain
perfectly parallel. (Hence the repeated SIJ88esliOns 10 rt!lax above.) If you find that
you can achieve stereopsis more readily this way, fine: If it works, use it! But please
remember that the image you see will be inverted. For most purposes this makes no
difference, but if the image is a chiral molecule. the cross-eyed method will give tht'
percrption of the other enan/iomer from thl' ont portrayt'd.'
Problems
tU CoiiSlruct a chin! D, modd as shown. Thro!llh whic11 faces does the c, uis pass? In
viewi111the model as an example of D, symmetry (A 8), where are the sc:condary C 2 ues
thai plaCe it in :t dihedral II" up? How is it that the C, aroup lack$ these? Which e11a11tiomer
do you ha\'e? Do you have any problems constructina the other enantiomet? Does the
"tricl<" for constructing the second en:uuiomer aive you 1111y insight into symmetry operations and chirality?
H.2 Construa a model or buckminsterfullerene, "buckyball", accordioa to the ditcaions in the
reference in Footnote 2.
a. Tum to Chapter 3 and do Problems 3.32throuch 3.36 on the b:tsis of the model in your
hands. Use paper "slue-on's" or tiaht pencil dr:lwinp to indk:lle the osmyl groups or
Fig. 3.34.
b. Bromin:tlion of buckyball yields a derivative with t2 Br: molecules addina
bonds:
C.,. + 12 Br2 ....
dooble
(H. I)
The resultant st ructure has very hip and unusual symmetry, with the remainirc 18
double bonds shielded rrom :>ddition by the bulky bromine atoms. Suggest a structure.
H.J Tum to Chapter 12 and do Problem 12.28.
' For runher disciiSSion of stereopsis see Sc>e2kman. J. C. N"' Scitntlstlm. 78, 827: Chem. Britain.
1m. 14. t07; Johnslone, A. H.; Ld10t1, K. M.: St>eakman, J. C. Edw:. CMnt. 198t. 17. tn-173.
ln. Jensen. W. B. J.
due. I tal. J9. )85; Falk. D. S.; Bri D. R.; S4ork. D. G . Sttint IM
Ugltt; tfatper A Row: New Vorlt.. t916; pp 209-219: Smich. J. V. Chtnt. Rr. IJII. &8, t49-t82.
Tebbe, F. N.; Hariow. It L.: Chase. D. 8 .; Thorn. D. L.: Campbell. G. C.. Jr.; CaW>resc. J. C.;
Herron. N.; V0U111o R. J .. Jr.; Wasserman. E. Smnct 1, 1, 2J6. 822-ll$.
Append
I
IUPAC Recommendations on the
Nomenclature of Inorganic Chemistry
The standards of nomenclature in chemistry are pc-oposed by the International Union of

Pure and Applied O>emistty (IUPAC). The cunent edition (the IJiird)' for inorpnic
nomenclarure is
o/lnorgonk CMmistry: R<mnumdotions 1990. issued by
the Commission on Nomenctature offllC)(Janic Chemistry. Part I consisiS of289
and
it is to be followed by sewn! ocher parts of specialized nomenclaJUre. It is possible
therefore to include here only a very smaU fraction :IS a gener.ll guide to good usnge. Thus
the following moterial is intended to guide the reader through the pc-occss of usi" good
nomenclatural practice, but it is noc meant to be a subslitute fOr the
themselves.
The suiddines pc-esented here (or even the unabridged set in Ole Red Book) should not
be viewed as a rigid code but as an evolving attef11'llo clarify the process of rwming. Usage
must be by Consensus and It is interesting to note that whereas preceding editions of the
Red Book were entitled "Rules," the c,urrent edition consists of Recommendations.
The usage in our book has been as close to JUPAC nomenclature as i5 consistent with
good pedagogy. We have foDowed the IUPAC Rt!comfTI#ndations
in th05e cases in
which I hey conflict directly with current
usaae.l Students are 001 served well by
limling one type of nomenClature in the text while beinc
to reno! the oriGinul
literature in which they lind a ndicnlly different nomenclnture. The prime purpus.: or this
book is to illustrate inOflllllliC chemistry rather than the details of nomenctaluratlechnique.
The nomenclature has IJierefore been thot which would serve bes1 in tc11ching inorg:onic
chemistry and help Ole students in reading the ori&inalliterruure.
This
consis1s of shor1 excerpts from
/990.1 Our commcnls and other additions have been placed in square brackets ( ). Dele1ions have not been
marked, but every attempt has been made to keep the inoent of the Ofi&inal. Otherwise the
fodowinc are verbatim
of the
with the
of minoc
editing such as chanains (I) numbers in series (FonOies, Tables. and Examples) to make
' AD three editions have been published with red covers lind arc nicknamed Ihe " Red Book.
: A sun-mary of inorpric nornend8laJre rrom die Amerin pOiru of view may be found in Block.
8 . P.; PoweQ, W. H.; FcmeiWs, W. C. tnors:cnlc CMmlccl Nmntntlutur" Princlpws cnJ Prot:tiu:
Amcricu a-.ical Society:
DC. t 990. UnfOI'IIIIWidy, i1 went to prcu 1oo early to
incorporare the chanles in I he /990 IUPAC Rtcom-nJoJioiiS.

1990: Lc:lah. C. J ., Ed.: BlackweU Scien0 1990, lnlctMiional Union of Pure lind AR'Iicd Chemistry. Rcl)tOI!uc:cd
1 Nomrnclalurr of lnoFJonic Chmobtry:
liroc: Ol<Cord.
A-46
wilh pc:rmis.sion.
I IUPAC Recocmnendations
0 11
lhe Nomenclature of Inorganic Chemistry
A-47
them contirwous and (2) the spelling to confOf'm to American usase. e.a. nluminum (Efl;l.
aluminium), center (Engl. centre), cesium (EnG). caeliium), etc. Foocnotes not in squnre
brackets are footnoles from the Red Book; footnotes in square brackets have been added
by us. The Red Book consists of eleven chapters (wilh oombered subsections), which are
here abstracted as "sections"; cross references have aenernlly been omitted e>tcept to
these major sections, Section 1-1, Section 1- 2, etc.
We have occasionally placed older, often obsolete names in square brackets aflet" the
IUPAC name. / n no
urt' thest intended 10 bt recommended alternatives but merely to
be useful guides to the tJlder (and
current}literum,.
All chapters in the Red Book beain with much interesting historicnl and philosophical
material concerning nOf'nenclature. These make interestinG and educmional reading, but
!hey have nol been reproduced fOf' space reasons.
1- 1 GENERAL AIMS, FUNCTIO NS, AND METHO DS O F

CHEMICAL NOMENCLATURE
M ethods of Inorganic Nomenclature
Systems of nomenc:l.ahiR
Binary-type nomencltlturr. In !his system, the composition or a substanCe is spe

cificd by the juxtaposition or element group names, modified or unmodified. together wilh
appropriate rwmerical prefi>tes. ir considered necc$$1lry.
Examples:
I. scxlium chlOride [NaOI
2. sUicon disulfide
Coordination
This is an additive system for inorganic coordination
compounds which treats a compound as a combination or a centr.tl a tom with associated
ligan.Js (sec Section 1-101.
.rumples:
I.
[CO(N021,(NHJl.J
2. sodium
Suh$timtioe IK)nlt!lldtlum:. This system
e>tlensivcly ror .,11:anic compuunds.
but it hus all;o been used h> n:amc many inorgunic compounds. II is often based un the
concept of a purcnt hy.Jride modified by sub$litution or hydrQtlen atonth by gruups tmdi
cals). [Sec Section I-6.J
E.rnmples:
I. bromobutane [C4 H9 Brl
2. dinuorosilane [SiH1 F1 )
3. lrichlorophosph.-lne [PCIJ I.
1- 2 GRAMMAR
Introd uction
Chemical nomenclature may be considered to be a lan&IJllGe. As sucb. it is made up or
words and it ahould obey the rules of syntax.
Generolly, nomenclature syslems use a base on which the ruvnc is constructed. This
base can be derived from a parent compound name such as sil (from silane) in substitutive
nomenclarure (mainly used for Ofll'lnic compounds) or from a centr.d atom name such as
cobalt in additive I'IOCIIei1Ciature (mainly used in coordination chemistry).
A-48
IIUPAC Recommendations 001 the Nome01clature o f l01orgo01ic Chemistry
Names are constructed by joining other Wlits to these base components. Affixes are
syllables or nwnbers added to words or roots and I hey can be suffixes. prefixes, or infixes.
according to whether they are plnc:ed after. before, or within a word or root. Representative
examples are listed in (Table 11]. together with their meanings.
__
lable 11
A selection ol all;es used ;,

iocwga,;c and ewe- ic
,_,endo
-a
-ane
-ate
-io
-ite
-
_j
Termination wwel for skeletal replacement nomenclature: -oxa (0), -au

(N), -carba (C), -lhia (S)
Termination for names of neutral saturated hydrides of boron and elements
.'
of Groups 14 (IVA), IS (VA), and 16 [VIA): diphosphane ( .. P2 H 4 ,
diphosphlne]
"
... ,
Geoernl suffix for many polyatomic anions in inorpnic oomenc:llllure
_
(including coordination nomenclature) and in orp.oic nomenclature: _
nitrate, acetate, hexaC)'IUIO{mate.
,
._ ,
J
Termination for name of many acids both inorpnic: and orpoicaulfuric:
acid. benzoic: acid
.
,,
.i' , 1
Tamination for name of certain m00011omic anions: chloride, su1.6de
Termination for names of the more dectroneptive constituent [atom or
group] in binary type names: dlsulfur dichloride; triiodide; cyanide 1-Termination for trivial name of
hydrides suc:b as NA and PH]:
hydraz.ine. phosphine
' -H- ...
f
General tenninaliclli for radM:als and substituent
an kinds '"1!'
containing a metal center from wtlidl the linkage is made: cuprio-,
methylmercurio-. tetracalbonylcoballio- ,fo', ':-..
,.
Termination f()( esten and salts of certain o"olcids havina the -ous ending
in the acid name: sulllte [from sulfurous acid] - ,
..:
""'
-t
y..,;......
----- .
"'""
("'.,..
""""''r...-,.a..................
," j
"' P
Termmabon for many elec:ttopoSJUve cooelitueli!T'ciiliiiiirycype munes,

either inorganic: or orpnic, either systematic trivial ,...-:-: .
I
Termination iodicatins the addition or one hydrogen ion (or a positive"Blkyl :
aroup) 10 a molecular hydride or its subscitutfoo product; ammoniwn.

Termination or cations formed from metallocenes: 'ferrocenium
Termination indicating a neptively charged lisand: bromo-. UsuaUy it
appears as -ldo, -ito. ato

l
Termination for the names of many lnoraanlc
organic: radiCals: c:hloro-,
1
piperidine-,,
'
"
Termination for infixes to
hydroxyl aroups:' thio-,
-ocene
Suffix for the trivial names or
derivativeS: ferroeene f
Termination indicatins'
dHi;),;t;vOI.nr
or
.?
'
1-3 ELEMENTS, ATOMS, AND GROUP OF ATOMS

Names and Symbols of Atoms
The IUPAC-approved names of the atoms of atomic numbers 1- 109 foc use in the English
language are lisred in a lphabetical order in (rhe table inside the back cover].
Indication of Mass, Charge, and Atomic Number Using JndeJCes (Subscripts
and Superscripts)
Mass, ionic charge, atomic number, (and molecular formula) are indicated by meoos of:
left upper index (supen;cript]
left lower index [subscript)
right upper index [superscript)
[right lower index (subscript)
mass number
a tomic number
ionic charge
molecular formula)
E.xmnple:
represents a doubly [positively] ioniucl {tetrasulfur cation composed ol] sulfur
alom[s) or atomic number 16 and mas.s number 32.
lsotypes
lsolypes ofhydrozen. The three isotopes. 1H. lH. and 'H. have the names 'protium'.
'deuterium', and 'tritium', respectively. It is 10 be noted that these names sjve rise to rhe
names proton. deuteron, and lri1on for the car ions 1H+. 1H , 3H . rtllpectively. Because
the name 'pcoton' is often used in contradictory senses. or iS()(upically pure 1H ions on
the one hand . and of the na.turally occurring undifferentiated iSOiope mixture on !he other,
!he Commission recommends that the L'llter mixture be desil!l'lated generaDy by the name
hydron. derived from hydrosen.'
Name ol an elemtnt ., el..-lllary subJt.nce ol dellnite molecu lar fOnnula

rure. These are named by adding the appropriate numerical prefix [see above) 10 the name
of !he atom to designate the number of atoms in the molecule . The prefix mono is not used
excepl when the element docs not normally e xist in a monoatomic stnte .
.ramplr:s:
Symbol
H
2. 0 ,
I.
J.
o;
4. P4
Trivial naone
s,.r......ric,_,.
;uomic hy.Jrogen
oxygen
ozone
while phosphorus
(yellow phosphorus)
trioxyacn
tetraphosphorus
a-sulfur, p..suii\Jr
(plastic sulfur)
octasulfur
palysuii\Jr
tNot al or these sub- and superscripts wiU nonnlllly be uoed one l ime. ThiiS we moy have
the IUPAC example, or we mil)lt have
for che tet,_..ruri2 i') calion. I
f..s!.
(This is a new recommendation. Note !hot it irT.,Iica t hat all uset wilh respeCI 10 IICids and bucs
involvi,. l.he normal isolcPc: mblure of 1H, 2 H, ond ,H WOIIId require the usc of hydron. I.e .. the
hydron alinity ol'ba.scs. BI'JIIISICd acids are hydron donon. etc. We have retained Ihe current usaae
ol' ""'"'" alinity, ete.,
the recommendalion came OUI as lhiJ book was aoitW 10 lftSS The
.--let should 100te howeva- dial hydron ia already receivinc satne European usaae. as in:
=
GSH debydronaled allhe thiol ........")
-cs-
A -SO
I IUPAC lecomme..dations on the Nom...dotur ofl.,orvonN: Chemistry
1-4 FORMULAE
(This section conlains considerable material on the proper writina of formulae , much of it
routine, some of it hiahly specialized. Most of the indicators of the number of atoms,
oxidation states, ionic charae. optical activity, and structures are very similar to those for
names and will be discussed in later sections, especially Section 1-10.]
Free radicals. IUPAC recommends that the use of the word radical be restricted to
species conventionaUy termed free radicals. A radical is indicated by a dol as right
superscript6to the symbol of the element or eroup. The formulae of polyatomic radicals are
placed in parentheses and the dot is placed as a riaht superscript to the parentheses. In
radical ions, the dot precedes the challl
I. H "
S. Br
2. (CN)"
6. [Mn(CO),I"
3. !HaCN)"
1. (Sna)r
4.
<o:r-
8. (OJ ..
Slntclurnl modifiers. Modilicrs such as cis-. trans , etc .. are listed in [Table 1-6: see
also page A-691. Usually such modifiers are used as italic:iud prefixes and are connected to
the formula by a hyphen [cis, trOJU-, etc.I.
Examplu:
I . cis-[PICiz!NH,hJ
2.
Sequence of Citation of Symbols

Priorities
Gl!nerol. The sequtnce of symbols in o formula is always artlitrary and in any

particular case should be a matter of convenience. Where there are no overriding requiremenls. the guiddines summarized (in Table 1-21 should be used.
Electronegativities and citation order. In a formula lhe order of citation of symbols is
based upon relative electronegalivities, the more dec1r0p0sitive constituenl(s) being cited
first . In the formulae or
acids, acid hydrosen is considered to be an dec
troposilive constituent and immediately precedes the anionic constituents.
Exumplu:
I. KCI
s. caSO.
2. H Br
6. (Ca1H10>(JCIJ
3.
4. NaHSO.
7. HJAuO.J
8.
Toblel-2
Assignment of fomdoe
of COIIIf'OU"cfs
(11 may be IIOICd here !hal very oftn in lhe p..a lhe ftu ndicaJ dot wu set
tlwl as a .._-scrip!.)
w (H I naher
I IUPAC Recomme..dotioes on the
Cbaln contpOUIIds.
of hoorgo11it Ch...istry
A-51
For chain compounds containina three or more different de-
ments. the sequence should generally be in accordance with the orckr in which the aiOrnS
are actually bound in the molecule or ion .
E.xnmplu:
I. - SCN (not CNSI
2. HOCN (cyanic acidl
3. HONC (1\Jirninic acid)
Pol,yatornic Ions. Polyatomic ions. whether complex or not, are treated in a similar
fashion. The central atom(sl (e.g . I in (ICI.r, U in Uoi . Si and W In [SiW110.,,1'- 1 or
characteristic atom (e .g. , Cl in CIO - . 0 in OH - 1 is cited first and then the subsidiary
groups follow in alphabetical orde.- of the symbols in each class.
1.
6.
so;ue>i
4. [P1w,.o111)"9. (Mo4o,.,f-
2. NO;
1. ao-
S. [BH.r
10. [IOJ-
Polyalomlc: c:ompo41nds or &I"OUJ)S. It is necessary to define the central atom of the

compound or aroup. and this is always cited first If two or more dilf..-ent atoms or gr011ps
are a ttached to a sin]e atom. the symbol of the central atom is followed by the symbols of
the remaining atoms or groups in alphabetiC31 orckr. The sole exceptions are acids. in the
formulae of which hydrogen is placed first. When p;lrt of the molecule is a aroup. such as
which occurs repeatedly in a number ol different compounds, these groups Olii.Y be
treated as forming the positive part of the compound.
I.
2. POOJ or POJO
3. HJPO
4. Sb01F
CoordinalkJn
(In the formula rA a coordination entity,) the symbol ol the
central atom(sl is placed first, followed by the ionic and then the neulr.llligands . Square
brackets are used to enclose the whole coordination entity whether charged or not . This
practice need not be used for simple species such us the common ox08nions (NO;, NOC.
OH- . etc .). Enclosing marks are nested within the square brackets as follows: !Iii,
!lOll. [{[OJ}). IIIIOD}). ecc.
A structural formula of a licand occupies the srune place in a sequence as would its
molecular formula.
1.
2. IAI(OH)(HlOisf
4. d.,..[PtCI:(P!C!HJllhl
S. N;t(PtBrt.:I(NO:lNHl)
3. [Ru(NHl),IN: liCI:
6. [PtCI:<C,H,NJN H,)"
Abbretiutiolls. These may be used to rcpre5enc liaands in formulae, and they are
cited in the same place as che ronnulae they scand for. The abbreviations should be lower
case. and enclosed in parentheses. Some commonly used abbreviations are in [Table 1-5.)
E.xnmplu:
I. [Pt(py)4 JlPtCI4 )
2. (fe(en>J[Fe(COJ.I
l.
The commonly used abbreviations for organic aroups, such as Me, Ph. Bu. etc . are
acceptable in inorganic formulae. Note that the dilference between an ooion nnd its parent
acid must be obsuved. Thus acne is an ocxcptuble abbreviation for acetylacetonaJe.
Acetylncetone (pent.a ne-2,4-dione)then becomes HICac.
7 The
hydroide ion is rqresercd by IlK symbol OH-,

l'ormulac or .octs would soaest HO-. Eample 3 accords v.ich
[Note tbal in Ibis
lhe cis-lrans isomer is nol specil\e<l.)
lhe ra:0C11111Ct10Wian for cbe

pndice.
A-52
I IUPAC Recommendations 0 11 tile
... dotu,.. af lnorga01ic Che"'iat.y
Addldon compounds. In tile formulae

compounds. the component molecules
cited in der of increasina number, if they occur in equal numbers, they are cited
in
order of the first symbols. Addition compounds containing boron compounds or water- nre exceptional, in Illat the water or boron compound is cited last. If both
are present. the boron precedes water.
Examples:
I. JCdS048H!O
4. C.H6 NH1 Ni(CN)2
2.
S. 2CH10HDF1
3. Al2(S0.)1 K2 S0.-24H1 0
6. BF12H10
1- 5 NAMES BASED O N STO ICHIO METRY

Names of Constituents
Elcdr opos;tin coDSCilvellls. The name of a monoaromic decrroposilive constituent is
simply the unmodified element name. A polyatomic conscituenl assumes !lie usual calion
name. but ceruin web established
names (particularly for oxyaen->ntaining species such as nitrosyl and phosphoryl) are stillnDowed for specific cases.
Examples:
I. NHQ
J. uo1a 1
ammonium chloride
2. OF1 oxygen difluoride
dichloride
4. 0 2F 1 dioxnen difluoride
S. POCI1
phosphoryl trichloride 6. NOCI nitrosyl chloride
7. 0 1 [PtFJ dioxygen heJUIJiuoroplluinaJe
Monoatomk dectrOIIepl.hl constltua!U. The name of a monoatornic electroneaative

(-en, -ese, -ic, -ine, -ium. -oaen. -on. -crus.
conslilucnl is the clement name wi!lllts
um, -ur, y. or -yaen) replaced by the anion designator -ide.
Examples:
I. chloride derived from chlorine
2. cartide derived from carbon
3. rung.stide derived from tungsten
4. arsenide derived from arsenic
S. ilicide derived from silicon
6. hyd ride o.lerived from hydr01;en
7. oxide derived from oxya;en
8. phosphide <lerivc<l from phosphorus
Finally. there are monoatomic anions whose names in EnJ)ish, though derived as described
above. are based on the Latin root of the element names. [See table inside back cover.] In
these the ending -um or -ium is replaced by -ide.
Examples:
I. auride-aurum- gold
3. scannide-SialliWm-tin
2. plumb4de- plumbum- lead

4. natride- narrium-sodium
HomoaiA>mlc eledr-onegatlve constiMnta. These have !lie name of !.h e monoatomic

parent . bur qualified by a multiplicative prefix. if appropriate. It may be necessary to use
parentheses to emphasize subtle poinr.s of structure.
'[Ahhoulh I he Lalin 11111rium ho.s been around

lof-c eimc. che IUPAC has noc recomcnended ics
use
and Na- has been univcrsaU.y calcd ''sodick. In view of che pt.sina ouc of terms
like "cuprous" and "fcnic." the incrodudlon c( hilheno urwsed latiniud IW1IeJ is unupccted.l
tIUPAC Recommendations on the Nomenclature of lnorgonic Chemistry
E.ramplu:
1.
tetrasodium (nonastannide)
A-53
2. Tl(t _,) thallium (triiodide)JO

4.
sodium disulfide
3. TICI3 thallium trichloride 10
Heteropolyatomic dectroncgalie conslilua!IS. The names of these anions take the

tennination ..ate, though a few exceptions are allowed (see Examples .5-16 below). The
ending ..ate is also a characteristic ending for the names of anions of oxoacids and their
derivatives. Tile names sulfate, phosphate , nitrate, etc., are general names for oxoanions
<XXllaining sulfur, phosphorus, and nitroge.n surrounded by ligands. including oxyaen.
irrespective of their nature and number. The names sulfate, phosphate. and nitrate were
originally restricted to the anions of specific oxoacids, namely
NO). but this
is no longer the case.
so!-. J>O!.
E.ramp[t!s:
I.
trioxosulfate, or sulfite
3. NO; dioxonitrate. or nitrite
2. SO!- tetraoxosulfate, or sulfate

4. NO) trioxonitrnte, or nitrate
Many names with -ate endings are stiU allowed, though they are not completely in
accord wilh the derivations outlined above. Some of these are cyanate, dichromate,
diphosphate. disulfate, dithionnte. fulminate, hypophosphate, metaborate, metaphosphate,
metasilicate. orthosilicate, perchlorate. periodate, permanganate, phesphinate. and phosphonate. The exceptional cases where the names end in -ide or -ite rather than -ate are
exemplified below.
Examples:
S. CN8. NH;
II.
14. NO!
cyanide
nmide
arsenite
nitrite
6. NHNH.- hydr.azidc
9, NH 2 - - imide
12. Cl01
JS.
chlorite
sulfite
7. NHOH- hydroxyamide
hydroxide
hypochlorite
16. S:O!dithionite
10. .QH13. CIO-
Indication of Proportions of Constituents

Use or multiplicative prefixes. The proportions of the constituents, be they monoatomic or polyatOmic. may be indicated by numerical prefixes (mono-. di-. tri-. tetra-.
pema-. etc.) as detailed in ffable 1-3). These precede the names they modify. joined
Tobie 1-3
I mono
13
2 di (bis)
14
:3. tri (tris)
:
' ;< IS
4 tetra (letrakis) f' J.
16
S pe.nta (pentakis) ' '
11
, 6 .;. hexa (hexakis)
18
n
19
lrideca
teUadeca
30 triaconta
31
-;_35 . JH:nu,trjac_onu
heiadeca '
';.;;
..
oo The use or oidalion stale clcsianallln would be lljlp<Opri3te. [Tlle parentheses :uound "triiodXIc"
distinsui$hcs n(I.Jl- ftom nl"31-.)
A -54
IIUPAC
on the Nomendature of lnorvanic Chemistry
directly without space or hyphen. The final vowels of numerical prefiltes shoukl 1101 be
elided, e.xcep( for
li,.uistic reasons. N01e that monoxide is an exception.
Where the compounds conlain elements such that it is not necessery to stress the proportions. for instance, where the oxidation states arc usually invariant, then indication proportions need not be provided.
1. Na,S04
2.
caet,
sodium sulfate. preferred to dlsodium sulfate

calcium chloride, preferred to calcium dichloride
The prefix mono- is always omiued unless its presence is necessary to avoid coofusion.
Examples:
I. N,O dinitrogen oxide
3. N 20 4 dinitrogen telrooxide
2. N01 nitrogen dioxide

4. Fe3 0 4 triiron tetraoxide
s. s,a, disulfur dichloride (sulfur monochloride)
6. M'nO, manganese dioxide
7. CO
carbon monoxide
The use of these numerical prefixes does 1101 all'ect the order of citation, which
depends upon the initial letters of the names of the constituents.
However, when the name of the constituent itself stariS wilh a multiplicative prefix (as
in disulfate, dic:hr&mate, triphosphDte, and tetrubotale), two successive multiplicative
prefixes may be rlecessary. When this happens, and in other cases s imply to avoid
confusion. the alternative mulliplicative prefilles, bis-, tris-, 1eiJ"alcis-. pentakis-. etc. are
used (see Table 1-3) and the nameofthearoupacted upon by the alternative prefix is placed
in
I. Ba[BrF4 J., barium bis(tetraftuorobromate)

2.
thallium tris(triiodide)
3.
uranium bis(disulfate)ll
1-6 SOLIDS
IThe Red Book has a twelve-page section of recommendations with respect to solid state
nomenclature, defects, phases,
etc. Very little of
material is uprticable to this book, so the section has been omilled because of space .)
1- 7 NEUTRAL MOLECULAR COMPOUNDS

Substitutive Nomenclatura
Introduction. This is a method of naming, commonly used for organic compounds, in
which names are based on that of an individual parent hydride, usunlly ending in-ane, -ene
or -yne. The hydride name is understood to si&nify a definite fixed population ofhydrocen
atoms attached ro a skeletal structure.
"[Note lhe di&ra>c:e bd-.n diaJIIIItc.
HSOi.l
Wsulfllle, an older, unsyslcm:Wt name for
IIUPAC Reccm-ndaticns en the Ncm.,.clcture cll110rgcaic Cltemiatry
ASS
Hydride names
Names of mononucletJr hydrides. Sub5titutive nomenclature is usually conJined to

the following central elements: B, C,Si. Ge. Sn, Pb, N, P, As, Sb, Bi . O.S, Se, Te, Po. but
it may be extended to cenain halogen derivatives. especially those of iodine.
In the ab5ence of any designator. the ending -ane signifies that the skeletal element
exhibits its standard bonding number. namely 3 for boron. 4 for Group 14 [IVA) elements. 3
foc the Group IS (VA) elements. and 2 for the Group 16 [VIA) elements. In cases where
bonding numbers other than these are exhibited. they must be indicated in the hydride
name by means of an app-opriate superscript appeflded to the Greek leiter A.'! these
symbols being separated from the name by a hyphen .
Examples:
I. PH1 A1-phosphane
This use of lambda applies to the -ane names but not to the synonyms for these names.
[That is. PH1 can be phosphane (systematic I or phosphine (nonsystematic). but PH, can be
only A' -phosphane;
is not permiued.]
Names of
ltydriJu Juived from t!ltmrnts of standanl bonding numb".
Names are constnocted by prefixing the ane names of the corresponding mononuclear
hydride with the appropriate multiplicntive prefix (di-, tri-,tetra-. etc.) corresponding to the
number of atoms of the chain bonded in series.
Examplu:
I. H.PPH, diphosphane (diphosphine]
tetrasilane
3.
2. HSeSeSeH triselane
4. H3SnSnHl tlistannune
1-8 NAMES FOR IONS, SUBSTITUENT GROUPS AND

RADICALS, AND SALTS
Cations
N"'""s of monoatcmic ations. Monoatomic cntions are nametl by adding in parentheses aft.:r the name of the element [either the appropriate chruye number followed by the
plus sign or tho: oxid<uion number (Roman numerall) followed by the words 'cation' or
;..lfl.
E.mnopl.-s:
I. Na
2.
3.
cr'
eu
4. cu'
s. u"
sodium( I +) ion, sotliumll) o:atiooll

chromium(}+) ion. chromium(! Ill cation (chromic)
coppeo11 +) ion. copper(!) cation
(cuprous)
cappeo12 +) ion. copper( II) cation
[cupric)
uranium(6+) ion. uranium(VI) cation
Names of polyatomic cations

Hrnn(}polyatomic cations. The name for a hornopolyatomic cation is (also the name
of the neutral species plu.s the charge number or oxidation number in parentheses!.
12 For o fuller discussion of the lambda coovention, see
IIppi.
1984. S6. 769.
" When there is no ambiguity about the charge on a Clllion. It may be omilled. e.g .. aluminum ion for
atuminum(3 +) or sodium ion for sodium( I + ).
14 Older names such as chromous for chromium(lll, cupric for coppcr{ll). and mercuric for mcrcury(ll) [and the other older names in bracl<ets above] are no longu-
A-56
I IUPAC IKommendatioas on thoo Nom.,.dature of laarga.,ic Chemistry
E.rtzmples:
I. !O.t
2. 1s;r
J.
dioxygeo( I +) ion (dioxyaenyl)

letr11Sulfw12 +) ion (This would be "cyc/o-tetrasulfurt2 + )" in the known
species.)
dimercury(2 +) ion. or dimercury(l) cation (mercurous)
Cations obtained formally by the addition of hydrotl.f to binary hydrides.s The name
of an ion derived by adding a hydron to a binary hydride can be obtained by adding the
suffix -ium 10 the name or the parent hydride, with e lision of any final 'e'. For potycalions.
the suffixes -diium, -triium, etc., are used wilhout elision of any final 'e'.
Ext.unplt!S:
I. N2H;
2.
diaz.anium. or hydruinium
diaz.anedium. or hydra:zinium(2 +I
Altt!rnative names for c:atiOtl.f obtained fomtDIIY by the addition of hydrotl.f to mononadear binary hydrides. Names for these simple cations can be derived as described
above. Alternatively . they may be named by a dding the endina -onium to a stem of the
element name.
The name oxonium is recommended for H,o as it occUfS in. for example. H,oao;
(hydronium is not approved)" and is resesved for this patticular s pecies. If the degree of
hydr.uion of the H+ ion is not known, or if it is of no particular importance, the simpler
terms hydron or hydrogen ion may be used.
E.ramplt!s:
1. NH; ammonium. or a:zanium

J . PH; phosphonium
2.
4.
H,o
H,s
oxonium
sulfonium
CoordinatiiNI cations. The names of Gornplex cations are derived most simply by
using the coordination cation names (sec Section 1-1 0). This is preferred whenever ambiguity might result.
Special cases. There are a few cases where trivial, nonsystematic or semisystematic
names arc srill aDowed. Some particular examples are shown.
E.wmples:
1. NO+
J . N02
nitrosyl cation
nitryl cation
2. OH +
4. [HOC!NHzlzt
hydroxylium
uronium
Anions
Monoatomic Jand homopolyatomic) anions are named by replacing the tennination of the
element name by -ide [and adding a numerical prefix as needed). In many cases, contraction.\ or variations are employed, as exemplified belOw.
E.ramplts:
Systematic
I. H2.
J.
o:-
s!-
4. -
s. o;
lS
'"
hydride
oxide
sulfide
iodide
dioxi<le( I -)
hyperoxide. or superoxide
IHydroriwn
to be 111ed uclusivdy;, American texlboak.s. l
0! is callc:d
in bioc:hen'kal nomcnc:lo.ture. the Commission recommends the
use of the systematic name dicWde(t -), becluse the prefix
not
the same ..-rio&
in
Other common MmCS are no1
llUPAC Rec:ommendotioM on the Nomenclature of Inorganic Ch-istry
6.
7.
8.
o;
q-
9. N)
10. Pb:-
dioxide(2-)
peroxide
trioxide{ I - )
dicarbide(2 - )
ozonide
acetylide"
trinitride{ I - )
azide
A-57
oonaplumbide(4-)
There are several anions for which trivial names used in the past are no longer recommended. Other anions have trivial names which are 5till acceptable. A selection follows.
E.ramplu:
t.OW
2. Hs3. NH1 4. NH1
hydroxide (not hydroxyl)

hydrogensulfide{ I - )18 (hydrosulfide not recommended in inorganic
nomenclature)l9
Ncs- lhiocyanatelo
imide. oc azanediide
6. Ncocyanate:tO
amide, or az.anide
s.
Anions derived from neutrol molecules by loss ofone or more hydrons. The names of
anions formed by loss orhydrons from structural groups such as acid hydroxyl are formed
by replacing lhe -ic acid, -ilric acid, or -eric acid ending by - ate. If only some or the acid
hydrons are lost from an acid, the names are formed by adding 'hydroaen'. 'dihydrogen".
etc., before the name to indicate the number or hydrons which are Slill present and which
can, in principle. be iomzed.
Examples:
I.
carbonate
3.
sulfate
co;-
so!-
2. HCO)
hydrogencarbonate( l- ) 1
4. HSO.O. hydrogensulfate(J-) or
hydrogentetraoxosulfnte(VI)
Anions derived formnDy by the ad.Jition or a hydride ion to a mononuclear hydride are
named using coocdination nomenclature (see Section 1- 10). even when the central atom is
not a metal.
I. BH;
2. PH,;"
tetrahydroborate( 1 -) (not tetrahydroboronate)lt

hexahydridophosphate( t -)
Coordi11ution ll<>mtnclature for httuopolyatomi<- anions. The names or pOiyatornic

anions which do not fall into classes mention! above are lie rivet! from the name or the
central utom using the termination -ate. Groups, including rnonootomic groups. attached to
"!This is the ''c::utide" ("c:alcium catt>idc") of '"carbide (acecylencl lamps."J

'" In the Nn,nclotuu nf Organic CMmistry. 1919 cdilion. hydrcscn is always used as a separalc
word. However. the names used here are oC coordination type. and differ.,. rules apply. In
inorpnic nomenclature h)'droaen is reaardcd as a calion in the names of acids unless the name is
intended to show that it is combined in an anion {as in the examples} above. (Inasmuch as the
hydroscn Is bound the same in H,CO,. dihydroscn carbonate (carbonic: :ocicl), as it is in HCO). the
h)'droaen carbonate anion. American
g<:ncrally put spaces hetween the words.I
19 Usc of the prefix mono-. to aive
avoids confusion wi1h hydrogen sulfide,
H,S. No1e that hydrosullide and hydroperoxidc is Joicl Slill allowed in Ol"J"nic nomenclature.
,. When coordinated in mononuclear coq>lcxes, lhese ions may bind throuan eilhcr end. This has led
to the use of the romcs isocyanate (-NCO vs. c}'llllale, -001]. etc to diSiinpsh the donor. This
usage ia disc:ouraacd. and the italicized donor symbol. namdy. cyanalo-C, or cyanaco-N. should be
employed. !See page A-n.]
ta 'Hydro' to represent 'hydrido' or 'hycJroaen is sanctioned by usage in boron nomcncla1urc (oce
Section I-ll). but is not to be U#d in other conlcxts.
A-SS
IIUPAC Recommendations o tt.. Nom. .dahl,. oll..o rgcrnic Ch...,istry
the centrnl atom are treated as lij:ands in coordinalion nomenclarure . The mme of the
cenlrnl atom, where not a metal, may be contracted.
Examples:
I. [PFJ-
2. [Zn(0H)4 )1 -
3.
[so.f-
4. [HF2 )-
hexaftuorophosphate{V), or hexaftuorophosphate{l-)
tetrahydrox07.incate(2 - ) [, 01'
tetr.Klxosulfate(VI), 01' tetraoxosutfate{2- )
diftuorohydrngenate(l -) (often named hydrngendiftuoride)
Even when the exact composition is not known, this method can be of use. The
rwmber of liaands can then be omitted, as in hydroxozincate, or zincate ion, etc.
OxoaciJ anions. Althoush it is quite practical to treat oxygen in the same manner as
ordinary ligands and U!!e it in the naming of onions by coordination nomenclature, some
names having the suffix -ite (indicating a lower-than-maximum olt.idation state) are useful
and therefore are still permitted.
Examples:
I. NO! nitrite
2.
ao-
hypochlorite
A fuD list of permiued alternative names for o xoacids a nd derived anions can be found
in (Table 1-4).
Substi1uent Groops
Radicols
Ddinltloas.. The term radical is used here in the sense of an atom or a group of atoms
having one or more unpaired dcctrons.
Systomatlc IUIIIIeS ol substltucat lf'lllps or radicals. The names of groups which can be
regarded as subslitumts in OI'Jilllic compounds or as ligands on metals are often the same as
the names of the correspoodi,._ radicals. To emphasize the kind of species being described,
one may add the word 'sroup' to the name of the species. Except ror certain trivial names,
names of uncha.raed sroups or radicals us ually end with -yl. Catbooyl is an allowed trivial
name for the ligand CO.
E:.ramples:
1. (CH, I- me.thanyl 01' methyl
2. (NO) nitrosyl
Ccrtoin neutral and cationic rn<licals containina oxygen (or cholcosens) have. reof charge, special names e nding in -yl. These names (01' derivatives of these
are used only to designate compounds consistinG of Jiscrne molecules or t;toups.
Prefixes thio-, seleno-, and telluro are aUowed to indicate the replacement of oxygen by
sulfUr, selenium, and tellurium, respectively.
E:.ramples:
1. HO
hydroxyl
2. CO
carbonyl
3. NOz nitryiU
phosphoryl
5. SO
sulfinyl, or thionyll>
6. S01 sulfonyl, or s ulfurylll
7. HOO hydrogenperoxyl, or perhydroxyl, 01' hydroperoxyl
8. CI"Oz chromyl
9. U02 uranyl
10. CIO chlorosyl
II. CIOz chloryl
12. 00, perchloryl
4. PO
12 The name nilroayl shooAd not be used for this VOUP hecauJe of the- oflhe lri.W name rilrox)'li<:
acid lilr H,NO..
::>The f - names :>re .,referred. buc I he tBIIer
The variant 10 be used in any paniaA:or
case dq>end$ on lbe c:irc:umstonccs. Thus. sulfuryl is used in inorpni<:
cbtuceanc!SIIM'onyt is used
is.orpoicchemisu tcnd 10
speak of rndhanesulfonyt cMoride, toleSOz(l. wtlik iootpnic chc..U.U Sf><*k of suWur}f cllloride.
-=:SO,Q,:,::....::_::-:::-- - -
IIUPAC Recomm.,.dations on tft Nomencla ture of lnorsanic Ch-istry
Such names can also be used in the names o f more complex molecules or in ionic: species.
E.ramples:
I.
2. PSCI3
carbonyl dichloride [phosgene]

thiophospt,oryl trichloride
3. NOCI
nitrosyl chloride
Salts
Definition ol a sail. A salt is a chemical compound consisting of a combination of
cations and anions. Howeve.-, if the cntion H,o is presem the compound is normally
descnl>ed as an acid. Compounds may have both salt and ocid character. When only one
kind of cation and one kind of anion are present. the compound is named as a binary
compound. When the compound contains more thun one kind of Clition and/or anion. it is
still considered to be a salt, and can be named following the guidelines betow.
When po(yatomic cations and/or anions ore involved, enc.losioglllari(s should be used
to avoid possible ambiguity. Thus 11t11 is thallium (triiodide) and 11111 11 is thallium triiodide. Alternatively, thallium(l) triiodide anclthallium(lll) triiodide would suffice.
Salts containing acid hydrogen. Salts contnininc both o hydron which is replaceable
and one or more metal cat.ions arc calletl acid salts. Names are formed by adding the word
'hydrogen. with numerical prefix where necessary. after the n:une of c:uion(sl. to l.lenole
the replaceable hydrogen in the salt. 'Hydroi;en' is followed withow space by the name of
the anion. In certain cases. inorannic anions may contllin hydrosen which is not easoly
replaceable. When it is bound to oxygen and it has the o xidation stnte of+ I, it will still be
denoted by 'hydrogen'. though s:Jits conlainiOG such anions cannot be designated acid
salts.
I. NaHC03
2. LiH!P04
) . K..HP04
4. CsHSO
!!Odium
lithium dihydro.:enphosphote
dipotassium hydrogenphosphate
cesium
or cesium hydrogentetraoxosulfatc(VI). or
..oxosulfate( I-)
cesium
1-9 OXOACIDS AND DERIVED ANIONS

Introdu ctio n
lnorg:mic chemistry is developing in such a wuy that
basel! on function ore disappearing. and nomenc:l:lture is
prefcmbly on compo1ition :ond
r:uher thun on
chemical properties. Chemical properties such as acil.lity depend on the
medium
and a cornpounll narnoo os an acill mif!llt well f\Jnc:tion :os a ba:oc: in some circumstances.
has a loogtradition anll it would be unrc:.listic to system
The nomenclature of
atize acill names fully and alter droslically the commonly acceptell names ofimportnnt and
well-known substances. However. there is no reason 10 proville trivial names which could
have a very limited use for newly prepared inorc;lllic compounds.
Definition of the Tllfm Oxoacid
An oxoacid is a compound which contains OJtyt;tn,
one other element, :u least one
hydroeen bound to oxyaen. nnll which produces a conjucate b:lse by loss or positive
hydrosen ion(s) (hydrons). Tile limits ofthis
of compou.nll ;ore dictated by
rather
than rules.
Oxoacids have been CJttensively used and studied and many of them therebe have
names established by a long prnctice. The oldest names. such as 'oil
vitriol I= coo-
or
A-60
IIUPAC Recommenclatiou on the Nomenclature of laorg...,ic O..mistry
centrated sulftric acid), are trivial. Later these nnmes were superseded bc:cause they we
round to be inconvenient and names reflecting chemicnl information, in this case the acid
property (as, for exnmple, with sulfuric acid), were coined. Names for the various deriva
lives of I he parents were developed from these names. This semisystematic approach has
limitalions. and has also led to ambiguities and inconsistencies.
Formulae
In a formula. the hydrogen moms which give rise to the acid property are cited first. then
comes the central atom. and finally tile atoms or groups of atoms surrounding the central
atom. These last are cited in the following order: oxygen atoms which are bound to the
central atom only. followed by ocher atoms and groups of atoms ordered according to
coordination nomenclature rules. that is, ionic liGands precede neutral ligands. Within each
class. the order of citruion is the alphabetical order of the symbols of the ligating atom.
rumples:
I. H:S04
2. H:SQ1
S. H4 P2 0 7 or
3. H2 SOs
4. H4 P20 6 or CHO)zOPPO(OH>z
6. HS01CI
Traditionol Nomes
History. Some traditional names (a selection is in [Table 1-4)) were introduced by
Lavoisier. Under his system, oxoacids were aiven a two-word name. the second word
being 'acid'. In the first word, the endings -ous or -ic were added to the stem of the nnme.
intended to indicate the content or oxygen, which is known today to be related to lhe
ox illation states or !he central atom. Unfortunately. these endings do nol
the same
oxidation states in different families of acids. Thus sulfurous acid and sulfuric acid refer
to oxidation states IV and VI, whereas chlorous acid anti chloric acid refer to oxidation
states Ill and V.
An extension or this system became necessary as more related acids were recognized.
The prefixes hypo- (for very low oxidation states) and per- (for very high oxidation states)
were introduced. The prefix per- should no1 be confused with the syllable in the ligand
name peroxo-. FinaUy. it became necessary to use other prefixes. ortho-, pyro-. and meta.
to distinguish acids differing in the 'content of water'. These traditional names do nol
provide specific information on the number oxygen ntoms. or the number of hydrOgen
atoms. whether acidic or not. The use of prefixes is nol always consistent: for instunce.
hypo- has been associated with the -ous ending (hyponitrous acid) anti with 1he
e.nding
(hypophosphocic acid). In the case of sulfur acids. two classes of ncid occur. one wilh the
stem sulfur and the olher with the stem 'thio'. Moreover. in substitutive nomcncbture
olher names such as 'sulfonic acid' for -SO,H. and "-sullinic: acid' for
were
developed. thereby forsaking the restriction -ic to the higher oxidation state.
As discussed above, the important chemical property
acidity is highly solventdependent. but a trnditional nomenclature emphasizes this property by using the word
'acid' in the name. The aim the systematic coordination nomenclature presented here is
to describe a composition and a structure. no1 a chemic:al property. Consequently. a
specialized word such as acid' has no place in it . This is the hydrogen nomenclature
{shown in Table 1-4). However. in recosnitionof current practice.the acid nomendature is
retained as an altemntive. This is only partly systematic.
or
or
or
or
Allowed traditional names for acids and their derilld anions. It is recommended that
retained trnditional names be limited to very common compounds having names estnblished by a long practice. Systematic names should be used for all olher cases. A list of
these traditional names which are retained for present use is given in (Table 1-4).
The use
-ous, -ic, per, hypo-. ortho-. and meta should be restricted to those
compounds and to their derivatives; their anions are named by chnngjng -ous into -ite and
-ic into -ate. In addition, and exceptionaUy, sulfur and phosphorus compounds lose the
or
Toblo 1-4
NomM for 'common oxoocids ond their Clftlons
Trodhionol nomo
ti);J,
boric acid
BO,>;
/.'2
melaboric acid'
l\ 4Si04
:.! , . orthosilicic
l(H1Si0J)- ,..
acid'
r HJCOJ
""'
carbonic acid
f HOCN
:t
cyanic ocld"
t HONC
..j
fulminic acid
JHNOj-;J,
nitric acid
llfN02
nitrous acid
,phosphlnic acid
i HlPOH .,
phosphorous acid'
,' 1=
phosphonic acid'
1 PHOl
l!I1PO
phosphoric acid
H.P10 7
diphosphoric acid
t(HP01l.
.melaphosphoric
_(HO)zOPPO(OH)i
hypophosphoric acid
arsenic acid
<arsenous acid
sulfuric acid
H2SJOia.,
disulfuric acid
.
lhiosulfuric acid
dithionlc acid
dilhionous acid
f 1SOJ
.
sulfurous acid
l'Jf
" -.J.
"'' chromic acid
r :r.:- dichromic
HCI04"'.
percl!loric acid
rH(;IOi ., -(
chloric acid
acid
r-1- .,.
acid
1
periodic acid
;tQ 6 !!A _ t " , orthoperiodic acid
f,1
H
l
til ...
I. "!lie lradilional name of Ihe
eolllupte onion In
Hydrogen
Acid nomoncloturo
trihydrogen lrioxoborate
poly[hydroeen dioxoborate( I - ))
tetrahydrogen tell'aOxosilicate
poly(dihydroeen trioxosilicate)
dihydrogen trioxocarbonate
hydrogen nitridooxocatbonate
hydrogen carbidooxonitrate
hydroeen trioxonitrate( l -)
hydrogen dioxonitrate( 1-)
hydroeen dihydridodioxophosphate( 1-)
lrihydrogen trioxophosphate(3-)
dihydrosen hydridotrioxophosphale(2 - )
lrihydrogen tetraoxophospbate(J -)
tetrahydrogen ,.,oxoheuoxodiphosphole
poly[ hydrogen lrioxophosphale( l - ))
tetrahydroeen hexaoxophosphale(P - P )(4-)
trihydrogen letraoxoarsenate
trihydrogen trioxoarsenale(3-)
dihydrogen tetraoxosul!ate
dihydrogen ,.,oxo-bexaoxodisulfate
dihydroeen trfoxothiosulfate
dihydrogen hexaoxodlsulfale(S- S)
dihydroeen letraoxodisulfate(S- S)
dihydrogen trioxosulfate
trioxoboric acid
polydioxoboric acid
tetraoxosilicic acid
polytrioxosilicic acid
lrioxocarbonic acid
nitridooxocarbonic acid
carbidooxonihic acid
lrioxonitric acid
dioxonilric acid
dihydridodioxophosphoric acid
trihydridotrioxophosphoric(2 -) acid
hydridotrioxophosphoric(2-) acid
lell'aOxophosphoric acid
,.-oxo-hexaoxodiphosphoric acid
polyt.rioxophosphoric
hexaoxodiphosphoric acid
letraoxoarsenlc
trioxoarsenic acid
telraoxosulfuric acid
,.,oxo-hexaoxodlsulfuric acid
trioxothiosulfuric acid
hexaoxodisulfuric
tetraoxodisulfuric acid
lrioxosulfuric acid
letraoxochromlc acid
,.,oxo-hexaoxodichromlc acid
tetraoxoehloric acid
trioxochloric acid
dioxochloric acid
monooxochloric acid
trioxoiodic acid
hexaoxoiodic(S - ) acid
hydrogen tetraoxochlorate
hydroeen lrioxochlorate
hydroeen dioxochlorate
hydrogen monooxochlorate
hydrogen trioxoiodale
penlohydrogen hexaoxoiodate(S-)
...
is formed: -lc:- l ie; -<lUS ... -ide.)
sianifies lhe acid wilh the maximum hydtlllion pcnslble, as HlPOc (CIS opposed lo HPO,l. H1 10 (as opposed to HI04 etc.)
'meta':' sianifies a dchydrotion product, as: nH)POc ('onho')
,..
!:
(HPO,I. ('mm'), etc:.)
......ls'normally
,
refen'rd to as ''phosphorous ecid" Is, by this system, a tautomeric mixture of "phosphorous acid" and "phosphonie
I;'HNCo; 1his acid is not an oxo:Kid sinee h)'llroaen Is not bound lo an oxnen 11om.
that
- .. -
A-62
llUPAC Recommendations "" the Nomenclature of Inorganic Chemistry
syllables 'ur and crus. respectively. from the acid nume when it is converted to the
name.
Polynuclear Acids
lsopolyacids (homopolyacids). Tilese materials are generally referred to in 1he lit<
aiUre as isopolyacids. The name hornOpOlyacids is preferable because the Greek root
homo- implies 'the same. in direct contrast to that ofhetero- signifying 'dilferenf. where
the rOOt of iso- implies equality. Detailed nomenclature of those compOunds has be.
presented elsewflen.z
Acceptable abbreviated names may be given 10 polyoxoacids formally derived l
condensation (with evolu1ion or wat) of uni1s of the same mononuclear oxoacid . provido
that 1he cen1ral atom of the mononuclear oxoacid has the highesl oxidntion state of 11
Periodic Grrup to which it belongs. that is, VI for sulfur, etc. The names are formed l
indicating with numerical prefixes lhe number of atoms of central element present. h is n
necessary to state the number of oxygen atoms.
E.tamplt'S:
t.
H,s,o7
2. H 2Mo601')
3. H6 Mo,024
4. H3 P,09
disulfuric acid. or dihydrogen disulfate [pyrosulfuric acid)

dihydrogen hexamolybdate
hexahydrogen heptamolybdate
trihydrogen cydo-lriphosphale [lrimetaphosphoric acid]
Heleropolyaclds. A detailed nomenclature of these compOUnds has been given el!

where.z Names are developed using coordinution nomenclature (Section 1-10).
E.tumplt'.<:
I. H 4SiW;:o040
2. H6 P2 w,.o62
tetrahydrosen hexatriacontooxO(Ietraoxosilicato)dodecalUili:Siate(4
hexahyllrogen tetrapentnconta
oxobis(letraoxophosphato)cx:tadecalungstate{6- )
Some abbreviated semitrivil names are retained for present use due to loog-slllndit
usage. This applies if all the central atoms are the same. if the p0lyanion contains on
oxygen atoms as ligands and only one kind of heteroatom. and if the oxidation state of l.
cen1ral a1oms cOrTespOnds to the highest oxidation stale of the Periodic Group in who
occur. In this usage. the Main Group atoms receive specific abbreviutell names r
incorpomtion into the hetero-polyacid name. These are:
B l>oro
Exnmplts:
I. H4 SiW120 40
2. H 6 P!W 1.Q62
Si silico
Ge I:Ctmano
P phospho
As ar.<en
tetrahydrogen silicododecatungslale
hexahydrogen diphosphoocladecatungstate
Ions Derived from Oxoodds

Anions. The hydrogen nomenclature name described above consists of two parts. II
second of which is an anion name . This can stand alone to represem the anion itself.
Traditional names are still accepted for the exceptions listed in (Table 1-41. The endi.t
-ic of the acid name becomes -ale in 1he anion name, and -ous becomes -ite.
Cations. The cations considered here are obtained by adding formally one or mo
hydrogen cations to a neutral molecule of Ihe acid.
E.tamplt':
I. (H,SO,J+
24
trihydroxooxosulfunVI) cation [sulfuric acidium cation!
See l'uu Appl. CNm. 198'7. 59, lS29.
I IUPAC lec:omm..,datio11 011 the Nomdoture of lnorga11tc Chemistry
A- 63
Note t.h at an elltension of the organic Slyle of nomenclature ns in

eth<lnoic
acidium. is discouraged because it is based on the word 'acid' and is often not easily
odapt3ble to languases ocher thnn Enalish.l.l
1-10 COORDINATION COMPOUNDS

Coordination entity. A <wrtlination emiry is compOsed of a central atom. usuully thnt
of 3 metal.to which is attached a suiTOunding array of other atoms or groups of atoms. ench
of which is caDed a ligand. In formulae, the coordination entity is enclosed in squnre
brllckets whether it is charged or uncharged.
Examples:
3. [ Fe,(CO)a:J
I. (Co{NHJ)JJ+
Central atcm. The cmtral utnm is the atom in a coordination entity which binds other
atoms or groups of atoms <lipnds) to itsciL thereby occupying a central pO>ition in the
coordination entity. The centrnl atoms in (Ni01 (H 10)4 ). (Co{N H3 ),j . and [Prcl.f - are
nickel. cobalt. and platinum. respectively.
Ugands.. The ligands are the a1orns or groups or atoms bound to the centr.d atom.
The rool of the word is often cooverted into other forms. such as to lil(utr. meanina to
coor\liRllte as a ligand, and the derived participles. lil/utinR and li11uted.
c-dination palyhedron. It i\
practice to think oft he
that nre
directly attllCbed to the centml atom as del\nirc a I.'<Jf>rdinutiun fJfl{vh..dmn (or pOlygon)
1
about the central atom. Thus (Co(NH 3>J'+ is un octuhedr.tl ion an.! [PtCI.J - is a square
planar ion. In this way the coordinalioo number may equal the number of vertices in the
c:<IOCdination polyhedron. Exceptions are common amonc orsnnometallic compounds.
E.tamplt's:
... .S: ,;.F [ C1c:JC1

PI ]: [ Cl ... co .... Cl ]:
.._ ...
C1
C1
F
I. ,-.-uhaJr;!l
C
..
Mft;U'c
rbn:tr
J..
k 1n.A.-.Irul
L'i)ltfdiNUiun
""'rh<.Jron
poly,...
Historicady. the concepts and nornencla1ure of coordination

were unamtime. but complications huve arisen more recenlly . Aooording to
trndition. every ligating atom or aroup WIIS recosniud as bringing one lone-pair of electo the centralntorn in the coordination entity. This shari nil of ligand electron pairs
became synonymous with the verb 'to coordinate. Further, in the inevitable electron
bookkeeping that ensues upOn con>ider:ltion of a chemical compound. the coordinaJion
entity was dissected (in Jhought) by removal of e3Ch li81111d in such a way that each lil;:lti"l:
atom or group took two electrons with it . Coordination number is simply definable who:n
such n thought process is applied.
biguous for a
u I.Howe..:r. as Ions as "sulfuric ncid" is the Dtlly n:ame used in the

ac:iciuoa c:alion''
on the previous IUPAC Red lloalcl will be
samedling trivial like "prot-.! sa.Uuric: acid. "I
for H;rSO . "sulfuric

unless we we
A-44
IIUPAC Recommendations on the Nomenclature ollnorganic Chemistry
Q)oo-dlnaUon number. As defined for typical coordination compounds. the coordinntion number e quals the number of sigma-bonds between tisnnds and the central atom. Even
though simple ligands such as CN-. CO. N 2 and P(CH.J1 may involve both sigma- and pibonding between the ligating atom and the central atom. the pi-bonds are not considered in
determining the coordination number.u
The sigma-bonding electron pairs in the following examples are indicated by : before
the ligand formulae.
Exomplu:
S. [Cr(:CO));-
.......0..
6
6
.,.,.,._.
Coon5natioft
CoonlinatiOft
Complex
I . [Co(:NH 1 )JJ+
3.
Complex
2 . [Fe(:CN),_f'4 . [Ni(:C0l4 )
6. [Col:0)4 l2 -
6
4
4
Chelation. Chelation involves coordination of more than one

pair
donor group from the same ligand to the same central atom. 11le number of such licating
groups in a single chelating ligand is indicated by the adjectives didentate,n tridentate,
tetradentate. penladentate. etc . (see (Table 1-3) for a list of numerical prefixes). The
number of donor groups from a given ligand attached to the same central atom is called the
Jenticity.
Exlll7lplt's:
2. didcn,..c cl>ctolion
4. I<V>d<nt:liC chdalion
Oxidation number. The oxidation number of a central atom in a coordination emily is

defined as the charge it would bear if all the ligands were removed along with the electron
pairs that were shared with the central atom. It is represented by a roman numeral.
Coordination nomenclature, an additive nomenclatun. According to a useful. historically-based formalism, coordination compounds are considered ro be produced by addi-
u This definition isappropri31e to codinalion compOUnds. bulnol no:eessarily 10 other :treas. such as
aySAalosnj>ly. (Nole also lhe s1rong depcndenc:c of this sySiem on the aswmo:d bonding modd.l
used bidcruate r:tther lh:tn didentale, for linauisJic consiSiency. In lhi edi1ion. a sinaJe set of
is used throuaflout and these
e listed in (Table 131. lBidenwe has been a pe<fecUy aood word in the e..Jish lanauage for 2.10
years or ITIOf"C, independent of chc.mi<lry. Unless one proposes to place the entire concent of the
languasc under the purview of the IUPAC. one must view this as a violalionofaood
thai
haS as Gnle logic os it does aood ctymoqy.J
Z1 Prc\'ious versions of !he Nomtntlolurt rif lnO<tonic
I IUPAC Rec:oonmenclations on the Nomenclature ol lnarganic Chemistry
A-65
tion renctions ond so they nnmed oo the basis of un oddilive principle. The name is build up
nround the cemrnl atom narne,just ns the coordiootion entity is built up around tile centrnl
ntom.
Ext1mplt':
I. Addition of ligands to a c:enrrnlwom: N;l+ + 6H:O- [Ni! H:O>.f+
Addition of lignnd names to a centrnl worn name:
ion
This nomenclature
to still more complicated structures where central atoms
are added together to form dinucl<!or. trinuclear. and even polynuclear species from some
mononuclear building blocks. The persistent
of the central utom is emphasized
by the root -nuclellt.
Bridging ligands. In polynuclenr species it is necessary to disti'l:uish yet anOther

lipnd behavior. the action of the ligand as a bridaing group.
A briclgi11g ligand bonds to two or more central otoms s imultoneou.s ly. Thus. bridgifll
ligonds link centml atoms
to produce coordination entities having more th:ln one
central atom. The number of centr"l atomS joined into a sint:le coordination entity by
bridgiflllit:a.nds or metal-metal bonds is indicated by dinuctear. trinuclear. tetranuclear.
etc.
Exomplrs:
I.
o...
/a., ...a
,-At,
:!..
Cl
/AI'
Cl
Cl
Formulae for Mononuclear Coordination Compounds
with Monodentote l igonds

Sequence of symbflls within the coordinalion formula. The ce nt roll ntom is listed first.
The formally a nionic ligands appear next and they are listed in alphubetic order according
to the first s ymbols of their formulae.
follow. also in alphOlbetical order.
according to the same: principle . Pol ydenta tc lil):tnds ;m: included in the alphabetical list .
Complic.Jtcol org;>nic li&alllls may be olcsitnatcd io fnrmulae with abbreviations [Tallie IS).
tJsH or enckl:<in.: onarks. The formuln fur the cn1irc coordina1it1n entity. whether
chargt:ol or not. is enck,.ed in S<jmlre
Whe n
ure poly:uomic . their formulo.e
are enclosed in parentheses. Ligand abbreviations ore ulso enclosed in punemheses. In the
special c-.tse of coordination entities. the
order of enclosures is a' &iven lon pupe
AS I). There should be no
between representations of ionic species within a coordination formula.
E.wmpln:
I. (Co(NH_,I,JCil
4. IPtCI(NH,CH, l!NH)):ICI
2. (Coa(NH1 ),JCI1
S. K:l PdCI.l
J. [CoCUNO:XNH1 l.ICI
6. [Co(en)J)CI1
Ionic: charges and .oodallon numbers. If Ihe formula of o charged coordin:uion entity
is to be written without thnt of the rounterion. the c:hu111e ill indicnted outside the square
bracket as a right superscript. with the number before the sign. The
number of a
c:entr.JI atom may be represented by a romun numeral used as n right superscript on the
element symbol.
Examp/t's:
I. [PtCIJl-
.:.
i H:edta :t _....,_,.
i Hlnta

H,ida
fd.lentl'>i-'5f!
'
rtmelt
" propylenediamine
::.1
Chelatlng and othor ligands
ethylenediaminetetrucctic acid
N,N.N' ,N",N"diethylcnetrilllllineperuaacetlc acid
nitrilotriacelic acid
troJU- 1,2-c:ycloheu.nediuminctetraacctic acid
lminodiaCCiic acid
-!f
trimethytenediamine
; tren !.
, tris(2-aminoethyl)amine
lriethylenetetramine
1,2-diaminocyclohexane
}hmta , ,..;.9'.;,. . hexamethylenetetramine
Hthsc, ..
thlosemicarbazide .
t depe
'{{;
1,2-bls(diethylphosphino)elhnne
salicylideneglyclne
( Hfsahn
i'
bls(salicylidene)-1,3-dlamimlpropane
r Hisaldien ; ..
bis(sallcytidene)dlelhylenclriamlne
bis(2mcrcaplobenzylidenc)ethyle nediamlne
, ... ...
-\..-
benzo-15-#own-5
. criptand 222
c ryptand 211
{l2)aneS 4 t .
!'Lt
Hztpp
Hlocp
:,:1
,PPIX
, ll8JaneP4 0 1 ._
.
( 14)1,3-dieneN4
Me.! 14)aneN.
cyclam
..
.....:-..
N.N.N'.N'te tramethylcthylenediamlnc
';
(1,2-ethanedlyldfnltrilo)tetraacctlc acid
(((carboxymethyl)imino)bis(ethanediylnhrilol)tetraacetic acid
troM-(1,2-c:yclohcxanediyldinitnlo)telraacctlc acid
lmlnodiacctlc acid
N-(2-amlnocthyl)-1 ,2-ethanediamlne
I ,2-ethanedlamlnc
1,2-propancdlamfne --w>
N ,N,N' ,N'Ictramethyl-1.2-ethaocdlamlne
1,3-propanedlamfne
.y..
N.N-bis(2-amlnoethyl)-1,2-ethaoediamine
N ,N'-bis(2-aminocthyl)-1,2-ethanedlamine
.; I
1,2-cyclohexanediamlne
1,3,5,7-tetraautricyclo{3.3.1.1 l-7 )decanc
I
hydrazinecarbothloamide
1,2cthanedfylbfs(dlethylphosphfne)
N-[!2-hydroxyphenyl)methyleoe)glycine
2,2'[1,3propnnediylbfs(nitrilomethylidyne))diphenol
2.2'-lminohls(l,2-ethanediylnilrilomethylillynl
2,2'-[1,2-ethanedlylbis(nilrilomethytidyne))dlbenunethio1
..
j
,..
I'
Mocroqocles
1,4,7,10,13,16-hcxaoxacyc1<XlCiaolecane
2,3-bcnzo-1,4,7, IO, Il-pentu('lxacyclopcntadec-2-cne
4,7 ,13,16,21 ,24-hcxanxn-l,llhlillzabicyclo[8.8.8Jhcxacosene
l,4,7, 10-tctrathlacyc1odollccnne
phthalocyanlnc
tctraphcnylporphyrln
o
OCillclhylporphyrin
protoporphyrin IX
,13, 16-tctmphosphacyclooctadccane
1,(8,1 ltetraaz.acyclotctradccanc
tctnmzacyc1otctradeca-1 ,3-dicnc
2.3.9,10-tctramcthyl-1.4.11,11 -lctraazacyclolctmdccanc
1
1,4,7,10, 13,1 6-hexaoxacycloocladccane

2,3,5,6,11,9,11,12-octabydro-1 ,4,7 ,10,13-benzopcntaoxacyc.lopenllldccene
4,7 ,13,16,21,24-hcxaoxa-1,Ukliazabicyclo(8.8.81hcxacosane
4,7,13,111tctraoxa-1,10-diaubicyclo[8.5.S)Ico$anc
. !
i
1,4,7,HHctrathiacyc1ododc;cane
phthalocyaninc
5,10,1.5,20-tctraphenytporphyrin
1\l
2,3,7,8,12,13,17 ,18-oclllcthylporphyrin
t;;f
3,7 ,12,17-tetrame thyl-8, 13-diviny1porphyrin2,18-dipropano1c acid
1,10-dfoxa-4,7, I 3,16-tet raphosphacyc1ooctudccane
1,4,8,11-tetraazacyclotetradccane
>J
1,4,8, I 1-teii'IUIZ3cyclotctradcca-1,3diene
2,3,9,l0-tctramcthyl- 1,4,8,11-tctraazacyclotelradccanc
1,4,8,11-tctrauzacyclotctradeca.nc
..,
1"
Table 1-5
Abbrayjcrrions for ligands and ligondlonnlng compoynd
Abbreviatioa'""w
Systematk
ComlftOft name
_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ __ _ _ _ __
DiketanH
).4.
_
..,. ....
acetylacctone
hcxanuoroacetylacctone
bcnzoylncctonc
1,1,1,2,2,3.3-hcptaftuoro-7
triftuoroacctylacetone
dibcnzoylmethane
dipivaloylmethane
2.4-pentanedionc
I,I ,I,.S,S,s-hexanuoro-2,4-pentanedione
1-phenyl-1,3-butnnco.Jione
6,6,7,7,8,8.8-hc ptanuoro-2,2-dimeth yl-3,5-octanedionc
1, 1.1-triftuoro-2,4-pentanedione
I,:Hiiphenyl-1,3-proplnedione
2;2,6,6-tetrumethyl-3,5-heptanedione
Amino r>lcohols
ethanolamine
triethanolamine
2-arnlnoel hanoi
2,2' ,2"-nitrilolriethllnol
lo
'....
&" ... ' ....
' pfrldine
py -:
lhf
Hpz
leifahydrofuran
:':" . .. ..
pyrazole
I
imidazole T
h erpy
2,2' ,2"-te,.Pyridine
a-picoline
,..c:
tctra(l-pyrazolyllborate(l-)
fiSn .
' isoalcotinamldc
fnia . t!
.;.:
nicotinamide fi
( pip = ...
pljleridine
. ..
Jutidlne
- .
c... 1
m-r-ti,t w
...
- - .. -
"
'
:.
..
II
I
La. -.-.... ....
pyridine
letrah)ldroCuran
l H-pyrazolc
IH-imidazolc
2,2':6' ,2"-lerpyridine
2-methylpyridlne
hydrogen tctrakls( IH-pyrazolato-N)borate(l-)
, 4-pyridinecarboxamlde
3-pyridinccarboxamide
piperidine
-.
2,6-dimcthylpyridine
JH-benzimidazole
-.i
.,.
'
....
A '8
IIUPAC Rec-
mendations on the Nomenclature of Inorganic Chemis try
Names for Mononuclear C oon fination Compounds

Monodentate Ugonds
with
of c:entnll atom and llgoncl names. The Hgands are listed in alphabetical
order. without regnrd to charge. before the names the central atom. Numerical prefixes
indicatirc the number ligands are not considered in detennining that order.
or
or
E.rumple{s/:
1. 4ichlorO(d iJ1henyiJ1hosphine)(lhiourea)platinumlll)
(2. t!ibTomol!isCtridlethyiJihosphine)jllatinum( II)}Z8
Nu...- of ligands i11 a coontiDatlon t Rtlty. Two kinds of numeriC:ll prefix a re available for indicating the number of ach kind or ligoncl within the name t.h e coordination
entity (see [T:1ble 1-3)). The simple di . tri-. etc . derived from c:arclinal numerals. are
genenlly recommended. The prefixes bis-, tris . tetrakis-. etc., derived from ordinals. are
used with complex expressions and when required to avoid ambiguity; for example. one
would use diammine but bis(methylamine) to make a distinction from dimeth ylamine.
When the latter multiplicalive prefixes are used. enclosina marl<s are placed around the
multiplicand .
marks are not required with the simpler prefixes di, tri-, etc. T here
is no elision of vowels or use a hyphen in tetraammine and similar names, except for
compelling linguistic rensons.
or
or
Termnalions for nMna ol caonlinatlon eotiti<S. All anionic coordination e ntities take
the encling -a&e, whereas no distinguishing termination is used for cat.ionic or neutr:ll
coordinat.i on entities.
nwnllers, O>Cidalloo numbtn, and ionic proportloes.. When the oxidation
number of the central atom can be defined without ambiguity. it may be indic:lted by
appending a roman n umernl to the central atom name.211 This number is enclosed in
after the part the name denoting the central atom. No positive sign is used.
Wh.:n necessary a negative sign is placed before the number. Arnbic uro indicates the zero
oxidation number. No space is let\ between this number and the rest the
Altc:matively. the Ch&rlle on a coordinwion entity may be indicated. The net CharJe is
wrillen in arabic numbers on the line, with the number preceding the charge sign, and
enclosed in parentheses. It follows the name the central atom without the intervention
or
or
or
or
a space.)()
Examples:
I. K.JFc!CNl,,l
2.
3.
4.
S.
6.
(Cu<NH)l,JO ,
(CoCI( NO:XNH)l4 )d
(Pt0(N H:CH,l(NH1):ld
(Cud,(O=C(NH:l:hl
7. K:z[Pdd4 ]
8. K1(0sdsNl
9. NalPtBrCI(N02 )(NH)))
potassium huacyanoferratc<lll
po1assium
-I
hexaamminecoball(lll) chloriole
pemaamminechlorocobalt(2 + ) chloride
tetranmminechloronit rito-Ncobah(lll) chloride
diamminechlorO(rneth ylamine)plalinum(l l) chloride
dichlorobis(ura)copper(l l)
po1assium tetrnchloropalladatc(ll)
polassium pentachloronitridoosmate(2-)
sodium amminebromochtoronitrito-N plalinate(l l)
l&[Tbe boklrlx:c ilalic tellers arc thcxlc ll6Cd in the n""'*llcul placement d liJand names. Olhc:r.
nondetamining leucn arc 11111rked with
29 [This is the Sloclc system o1 indkalina oxiclation sutc oft he mew (and ind'oreclly, cfwae on the
cornpcx). Slock. A. Anf{rw. Clvm. 191t. 17. 373.1
"'[This i the Ewens-Bassd1 s)'SI- ol indiealing char&c on the compkx land irdirer:tly, the
oidation stale of the meW). Ewens. R. V. 0 .: Bassell, H. Clvm. Ind. 1949. rT, 1)1.1
z.
I JUPAC lecomm..,dotions o" lfte
10.
I I. [Ru(HSO,):(NH,J.I
12. [Co(H 20J2(NH,JJO,
of l11orgo11ic Chemiotry
A-69
hexakis(methyl isocyanide)iron(lll bc-omille

telr.l.amminebis(hydroaensulfito)rutheniulll(lll
retraamminediaquacoball(lll) chloride
Stereochemical Descciptors3'
Different geometrical arrangements or the atoms auached to the central atom are possible
for aU coordination numbers greater 1han one. The coordina1ion polyhedron (or polygon in
planar molecules) may be denOicd in the name by nn affix called the pclyhedml symbol.
This descriptoc clearly distinguishes isomers differing in the ceome1rics of their coordination polyhedra.
Given 1he same coordinalion polyhedron. diastereoisomerism can :uise when the
ligands are n01 all alike as wi1h me cis and Irons isomers of telraanvninedichbochromium{ JI I). dianvninedichboplatinum( ll ). and bis(2-aminoethanethiolalo)nickel(ll)
(Examples 1-6).
E.xampln:
I.
O.lfiOII"Ct
Cl
'
a
/
Pr
' NH1
J. ell iloalCt
H,N...._
H,:-1
/NHJ
' "' Cl
'
tf'WisiJ;Umcr
/S
..,..NJ,
Nil!
CIJ,-Cit,
s.
Cl
/NH 1
lf'dtiS b.ontet
S..._
S
/NH 1
.,...:or.,
NH:
Cli, - cu,
b. ,.,Jbc.lt1ter
A1temp1s 10 produce descriplocs simibr to <'is and mms foc slereochemicolly more complicated coordination entities have fuilcd lo achieve senerality. and labels such nsjciC: and mnare no longer recommended. Ncvel1helcss. n diaslereoisomeric struc1ure may be indicated
foc any polyhedron using a c:orrfigurutlon indrx ns an affix 10 the name or focmula. FinaDy,
the chiralities of enantiomcric sJructures can be indicated using chirality sytnbtJis.
symbol. The polyhedrnl symbol indicates 1he geometrical ammsements of
the coordinating atoms about the central atom. It consists of one oc more capital italic
letters derived from common geometric terms which denOie the
geometry of the
ligands around the coordination center, and an nrnbic numeral that is the coordination
number of the central alorn. The polyhedral symbol is used as an affix. enclosed in
[A list otsacn:ochcmical descriplon- JINCIUrol prefixes
be focond in Table
n (Nole thel American chcmitts would noc ilaicizc c b - lr:ons (or roc and mcs')lliben 1101 pen of a
name. nor hyp.a-.te '"I tans isomer.-- See also Footnolcs )) and 34.1
Jt
A-70
IIUPAC Recommendations on the Nomenclature allnargonic Chemistry
Table 1-6
Sltvctwol prefixes .....! in

inargonic nan.>elature
untiprismo
eight atoms bound into a rectangular antiprism

a boron structure intermediate between nido- and hypho in degree
of openness. (See Table 1-8.)
asymmetrical
a chain structure; often used to designate linear polymeric
substances
two groups occupying adjacent positions, not now generally
n:convnended for precise nomenclature purposes
a cage or closed structure. especially a boron skeleton that is a
polyhedron having an faces triangular
a ring structure. Cydo here is used as a modifier indicating structure
and hence is italicized. In orcanic nomenclature, 'cycto' is
considered to be part of the parent name since it changes the
molecular fOrmula. and therefore is not italicized
eight atoms bound into a dodecahedroo with triangular faces
three groups occupying the corners of the same face ()(an
octahedron, not now gener.Uiy recommended for precise
nomenclature purposes
eight atoms bound into a he><ahedron (e.g.. cube)
twelve atoms bound into a he><agonlll prism
an open structure, especiaUy a boron skeleton, more closed than a
k/ado-structure, but more open than an arachne-structure
twdve atoms bound into a triangular icosahedron
a very open polyboron structure
meridional; tllree groups occupying vertices of an octahedron in such
.a relationstwp that one is cis to the two others which are
themselves trans, not now reoommended for precise nomenclature
arathno
asym
catrna
ds
closo
cyclo
dodecaltt!dro
fac
hrxahedro
hexaprismo
!typha
lcnsaht'tlro
/.:Iado
mer
purposes ___.. _ _
nidu
closed
si>< atoms bound into an octahedron
ten atoms bound into a pentagonal prism
four atoms bound into a quadrangle (e.g., square)
symmeuical
four atoms bound into a tetrahedron
two groups directly across a central atom from each uther. i.e . in
the polar positions on a sphere. not now generaDy recommended
octnhrdro
pentaprlsmo
quadro
sym
temtlrrdro
lrt.lns
: ...
trianguln
triprismo
p. (mu)
- - - --
a nest-like structure, especially a boron skeleton that is almost
for precise nomenclature purposes
. three atoms bound into a triangle

;"
'IJo
six atonls bound into a triangular prism
-.1 signifies that a group so designated bridges two or more centers of

. j .
ii _coordination .;;. ;( '!
_
_
'
). (lambdo)
,s uperscript. lhe bonding number. i.e., the
1
'
-::. .! -'f.i!: the number of skeletal bonds and the number of hydrogen atoms
r. -4f associated With an atom in a parent compound
1-
I IUPAC
0 11
lh Nome,.da ture af Inorganic
A-7 1
parenlheses, and separaled from the

by a hyphen. The polyhedrnl symbols for the
most common coordination geometries for coordinotion numbers 2 to 9 inclusive nre aiven
in (Table 1-7].
Confi&uratlon inde"
Definition of
and ussignment of priority numbt'rs to /ig111i11g atoms. Having
developed descriptors for the general geometry or coordination compounds, it becomes
necessary to identify the individual coordination positions. T he confiflurotion index is a
series of digits identifying the positions of the lignting atoms on Lhe venices o r the
coordination polyhedron. The individual configuration indu has the property that it
distinguishes between diastereoisomers. The digits of the configuration indeJl are established by assigning an order of priority to the liptinc atoms a s described (belowI.
The procedure for assigning priority numbers to the lipting atoms o( a mononuclear
coordination system is based on the standard sequence rule developed for enantiomeric
carbon compounds by Cahn, Ingold, and Prelo&. The ligating atom with hiahest priority is
assiaoed the priority number I, the ligating atom wilh the next hiahest priority. 2. and so
on.
Configuration illckxes ror partic:ul:w &eomdries
Squort! planar coordinmion I YSI<'IIIS (SP-.S/. The configuration index is a single digit
which is the priority number for the ligntinc atom trans to lhe li8Diina atom ol priority
number 1.
Tol>le 17
I.Ht of polyhedral oymbo&
Coonrnrtian
Coonlinotion
numMr
polyhedron
linear
angular
trigonal plane
lJiGonal pyramid
telrahet.lron
square plane
trigonal bipyr.unid
squnre pyramid
O<:lah<.'\lron
triguna l prism
pent:lgOIIDI bipyramid
octahedron, face monocapped
trigonal prism, sqoore race monoc:apped
cube
square antiprism
prism, triangular face bbpped
trigonal prism, square face bicapped
trigonal prism, square face tricapped
heptagonal bipyramid
doo.Jec.Jhedron
hexagonal bipyramid
J
,octahedron, trans..t>icapped
----------
(Note !hall <'ISIrdns tcrminui"Gy
L2
1\2
TP-3
TPYJ
T-4
SP-.S
TBPYS
SP YS
OC-6
TPR-6
PBPY-7
OCF7
TPRS7
4
4
s
s
1'1
6
7
7
7
is noc lldcqu:ue 10
square pluW cootdin:llion Cftily (Mobcdl.
2
2
..
Polyhecfooal
..,....,...
8
8
8
8
9
9
8
8
8
TPRS-9
HBPY9
the three is.xners ora
A-7't
IIUPAC Recommendations on the Nomendature of l..argonic Cheonith"y
Examples:
ISJ> -4 11(11Ceu>nilrileJdicllloro(pyriclinel.,..,inum(Ul
[SP4 f)(OCCioniuile)dichJOoolp)'ridinelpii!Jinumln)
Octahedral coordination sy.<ltm.r (OC-6). The confi(lurution index consisls or two

digits. The first digit is the priority number of the ligating atom trans to the ligating atom of
priority number I. These lwo li8111il1& atoms define the reference axis of the octahedron .
The second digit of lhe configurarion index Is the priority number of the ligating atom trans
to the ligating atom with the lowest priority number (most preferred) in the plane that is
perpendicular to the reference axis.
Exnmples:
Fo rmuloe and Names for O,elale Complexes

De.1&nntlon olthc ligallng atoms In
11
polydmlalc llgand
Donor atom symbol as the Index. A polydenlate lignnd possesses more th:111 one
donor site, some or all or which may be involved in coordination. Thus. dithiooxalate anion
conceivably may be attached through S or 0, and these were distinguished by dithiooxalato-S.S' and dithiooxalato-0,0'. respectively.
Examples:
I.
aI sl
[\/ys
2.
/'c.;
Ni
0 ..
"I -
bis(dithiooxalato-0 .o)nickd(ll)
,. 'The isomer
- -for
bis(dithiooxalato-S,S')plutinum(ll))
/and mu may he wdtd for &enenl dilcussiotw bul..-e no1 rccommend<d
I IUPAC Recommendorions on the Nomenclatvre at Inorganic Chemi.s try
A-73
If the same element is involved in the different positions. the place in the chain or ring to
which the central atom is attached is indicated by numerical superscripts.
E.wmplu:
I . (OilCOCHCOCH3)
2.
O=C-0
"-
2.4-pemanedionDio-Cl
O=c-o
I
3.
Hco---M
4.
k___.-M
HCO ...............
HCOH
o=c-o
I
O=C-0'
)-01,62
wtr.II0(4-)-CJ2.ol
/cuppu c:onwntion. As the complexity of the ligand name increases. a more

general system is needed to indicate the points oflis,ation. In the nomenclature of polydentate chelate complexes. single ligating atom attachments of a polyatomic lipnd to a
coordination center are indicated by the italic element symbol preceded by a Greek kappa,
oc. Monodentate ambident ligands provide simple examples. although for these cases the
kappe convention is nor significantly more useful than the 'donor atom symbol' convention
[above!.'' Nitrogen-bonded NCS [formerly isothiocyanato) is thiocyanatO-ocN and sulfurbonded NCS is thiocyanato-KS. Nitrogen-bonded nitrite [formerly nitro) is named nitrito-ocN and oxygen-bonded nitrite is nitrito-ocO, i.e.. [O=N-0-Co{NHl),i + is pentaamminenitrito-ocO-cobalt(lll) ion.
For polydentate ligands, a right superscript numcml is added 10 the symboloc in order
to indicate the number of identically bound ligating atoms in thef/t'xidemate-"' ligand. Any
<loubling prefixes. such as bis-. are presume<! to operate on the K locant index as well.
Examples [ I and 2) usc tridentate chelation by the linear tetraammine ligand, N ,N'-bis(2
aminoethyl)-1.2--ethanediamine to illustrate these rules.
rumples:
I.
[N.N' -bis(2..arnino-ocN-ethyl}-1,2ethanediarnine-KN)chJoroplatinum(ll)
2.
[N-(2-amino-ocN..ethyi)-N'-(2-aminocthyl)-1 .2ethanediamine-,;N,N')chloroplatinum(lt)
Stereochemkal
for cloelated complexes. Stereochemical descriptors can be
provided fOI' compounds containing chelated ligands but they involve considerations
beyond those described above. The polyhedral symbol is determined as in the case
of monodentllle ligand derivatives. Also. the priority numbers arc assigned to ligwing
atoms as for monodentate ligands. However. a gcncrol lreatrnent for the assignment
of the configuration index requires the use of priming conventions in order to provide
" !The chief advantaae of the kappa convention seems to be thai it woambif!UOUSiy dcnooes (jgati"'
atoms in a co!ll'lcx ligand. This distinguishes she lis tina 01om in an orgonic liJand that may have
organic d-.criptors. as in
,. Any dlelati"' lisand C3pobie of bildng with more than one set ol donor 81oms is described u
cl.. Slnllloci, W. J .; Busch, D. H. J. Am. Chtm. Soc. 1951,80. )191.
A-74
I IUPAC Recoonmenclotions on til NonNttdatur af lnorgonic Chonistry
a completely systematic treatmenc . Thus, for a particular diastereoisomer or

lhe polyhedral symbol is OC-6 and the Jipting atom
priority numbers are as shown below.
Example:
mom
(I)
' '
',
(2)
\.'
(I)
For lhis case, there are no additional eomplieolions, and the conflguralion index is assisned
in the usual woy as OC-6-32.
The classic ease of diastereoisomerism thai arises among chelate liGand derivatives is
lhe tris(didentate) complexes in which the two donor atoms of the identical ligands are
diffen:m. Glyeinate, NH2CH2 C02, and 2-aminoethanelhiolate,
illustrate
this. For complexes of either lig01nd, lhe facial and meridional labels described previously
rould be applied, but t.h e moo-e systematic confi&ur.Won indexes are OC-6-22 and OC-6-21.
Exumplrs:
I.B o,8
\/
, 8
.
B
'/
B
mcriclianol.
orOC-6-21
Priming convrntion. The configuration index is especially useful for bis(tridentate)

complexes and for more complicated cases. Bis(lridentate) complexes exist in three diastereoisomefie forms which serve to illustrate the utility of a priming convention. These
i'IOmers are represented below, along with their site symmetry symbols and configuration
in.Jexes. For Examples I, 2, and 3, the two liJ;nnds an: identical and the ligating-atom
priority numbers are indicated.
"'0''(
(I')
..
t2)
'
..
( I)
(2')
...
(I ')
-- 11)
. 1,'
(I)
......
... ; " :
(I)
.' /
12'1
(I')
(I ')
I. OC-6- t ' l'
2. OC-6 2' 1'
3. OC- 6 11'
(2)
Olirality Symbols
B and S. 1hue are two established and well-used systems for chirality
symbols and these diffes- in fUndamental ways. The first, the conven1ion for chiral c:art>on
atoms is equally appropriate to metal complexes llnd is most often used in conjunction with
ligand chirality. HoweVCT, it ean be
to metal cel\lers and hns been useful for
pseudo1etrahedcal organometallic complexes when, ror example. cyclopel'llodienylligomds
are trealed as if they were monodentate lipnds ol hich prioricy .
IIUPAC lec:ommendotiona on the Nomenclature of l10orgoooic
A-75
Skew-lne coovmtleo ror octahednl complexes. The second is the skew line convention and applies to octahedral complexes. Tris(didentate) complexes constitute n generol
Cnrnily of structures for which a useful unambiguou.s convention has been developed based
on the orienlalion of skew lines which define a helix. Examples I and 2 represent the delta
and lambda forms of a complex, such as [Co(NH2CH1CH2NH 2)J'.
--- 0 0
E:complt's:
....
....
...
..
I . ddto
[There follows an explicit discussion of the chirolity of oc:tahedrol complexes a.nd chelate
rings as summarized in Chapter 12.]
OUnlilJ symbols based on the priority sequence. The procedure is applied as for
tetrahedra, but modified because there is a unique principal axis . The slnlcture is oriented
so thnt the viewer looks down the princ:ipol nJ<is, with the ligand havins the higher priority
closer to the viewer. Using this orienwion. the priority sequence of ligillillG atoms in the
[horizontal] plane is ex:lmincd. If the sequence proceeds in a clockwise fashion. the
chirality symbol Cis assit;ned. Conversely. if the sequence is nnticloc:kwise. the symbol A
is assigned.
E:camplrs:
I. Chinlity symbol C
) . Cl>ir.liity J)'mbol
4. Cl>intny &ymbol " A
[An example of a renl compOund to which this system may be applied ill found on page 488.
cis-dicarbonylchloro(cyclopcntadienyl)(mcthyldiphenylphosphine)molybdenunttll ). The
enantiomer shown there has the chirality symbol C.)
Polynucleor Complexes
Polynuclear inorpnic
exist in a bewiklerins: array of structurnltypes. 5Ueh
as ionic solids, molecular pOlymers, extended assemblies of oxoanions both of metals nnd
nonmetals, nonmetal chnins and rins:s. bridaed metnl complexes, und homo- and heteronudeur clusten. This section treats prirmarily the
rc of bri.Jsetl metal complexes
and homo- and hetero-nuclear dusters.
Bridging Jigonds, as Cnr as they can be specified, ore indic..ted by the Greek letter p.
A-76
IIUPAC Reeonunenclations on the Nomendotun of Inorganic Chemistry
appearing before the ligand nwne and separoted by a hyphen. The whole term. e.g . p.
chloco, is separated from the rest o( lhe nome by hyphens. as in ammine-p.-chforo.chloro.
etc . or by parentheses if more complex
ore involved. The bridging index. the
number o( coordinution centers connected by a bridgina ligand. is indicated by a right
subscript. P.n where n > 2. The bridging index 2 is no1 normally indicated. Bridging ligands
are listed in alphabetic order along with the O!her ligllllds, but a bridging ligand is cited
before a corresponding nonbridging ligand. as with di-p.-c hloro-telfachloro.
I.
2. [{Cr(NH 1J,hlw0H>P5
3. [(PICI{P(C.,H,J1 1b(}l-CIJ:]
4.
bis(p.acetato)(cyclopenradienyl)(methyl)cobaltdicoppertin
p.-hydroxo-biS(pentnamminechromium)(S +).
pentachloride
di-wchlorobis[chloro(triphenylphosphine)ptatinumJ
bis(p.-diphenylphosphido)bis(dinit.rosyliron)
Metal-mew bonding may be indicated in names by italicittd atomic symbols o( the

appropriate metal atoms. separ.ued by a Ions dash and enclosed in parentheses, placed
after- the list or central atoms and before the ionic charge.
J-
I. [Br4 ReReBr
2. [M!C0)..,)
bis(tetrabrornorl\cnate)(Re- Re)(2-)
bis(pentl!Cllltlonylmancancscl<Mn- M n) or
clec=trbonyldimanc<lllese(Mn-Mn)
Organometanic Species
General. Organometallic entities are usually considered to include any chemical
species containing a carbon-metI bond. The simplest entities a re !.hose with alkyl radical
liaands. such as diethytzinc. In gencral.ligands bound by a single carbon atom to metals are
named by the customary substituent 8fOUP names. though these ligands must be treated as
anions in order to calculate oxidation numbers. In any case, the designation is arbitrary.
Ligands conventionally treated as having metal--donor double bonds (alkylidenes) and
triple bonlls (alkylidynes) are also given substituent group (radical) names.
E.xnmpll.'s:
I . [Hs(CH.Jhl
IIi methylmercury
2. MgBrjCH(CH!l!l
3.
4. (FeCCH,CO)I!CO)z(P(CH,l1hl
cyanodiphenyhhaUium
acelyldicarbonyliodobiS(trimethylphosphine)iron
Complexes with unsarurated groups. Sioc:e the first reported synthesis o( ferrocene.
the numbers and variety of orgnnometallic compounds with unsaturated organic ligands
have increased enormously. Further complications arise because alkenes. alkynes. imides.
diazenes. and other unsaturated ligand systems such as cyclopentadicnyl. C,H$. 1.3buladiene, C4 H6 , and cycloheptatrienylium. c,H;, may be forma lly anionic. neutral, or
cationic. The structures and bonding in some instances may be oomplu or ill-defined. For
t.hese cases. names indicating stoichiomiO!ric composilion, constructed in the usual manner,
are convenienl. The ligand names are arranp:d in alphabetical ocdcr, and followed by
central atom names, also in alphabetical order. Bondina notation is not given .
I.
2. (Hg(C,H,h)
3. (Fe4 Cu4 (C,H,>.{((CH,):N]C,HJ4 )
amminedichloro(ethene)platinum
bis(cyclopentadienyl)mercury
tetnkis(cyclopentodicnyl)letrakis[(dimclhylamino)cyclopentadicnyl)tetracoppertetrairon
IIUPAC Re commendations on tt.e Nomenclature ollnorganic Chemistry
A-77
The unique nalure of the bonding of hydrocarbon and other ...elearon systems to
me!als nnd the complex struc tures cf these entities have rendered conventional nomendature impOte nt. To accommodate the problems pOsed by lhe bondina and structures. the
hapco nomenclature symbol was devised.l 7 The hapto s ymbol. 'I (Greek eta). with numerical superscript. provides a topoloaical des cription by indicating the connectivity between
the ligand and the central atom. The symbol 'I is prefixed to the ligand name. or to that
p0nion or !he ligand name mOiit apprOpriate . to indicate the connectivity . as in
ethenylcyclopentadiene) and (ethenyi-TJ5-<yclopenllldienyl). The right superscript numerical index indicates the number of ligating atoms in the ligand which b ind to the metal
(Examples 4 to 10).
.rumples:
4. (Fe(C0)l(C4 H 6 S0))
S.
6.
7.
8.
[CrtCJH.J1J
[CrtC0)4 (C4 HJJ
[PtCI:CC1 H4 )(NH:J)
[Fe(CO)l(C,H.ll
tris(TJ1-allyl)chromium
tetracarbonyl('I4-2-methylene-1.3-propanediyl)chromium
(TJ-bicyclo(2.2.1]hepta-2.S-diene)tricarbonyliron
(uranocene)
dicarbonyl(l)5 -cyclopentadienyll{( 1.2.3-11)-2.4.6cycloheptatrienyl)molybdenum
r\
9. (U(C1 H.J1)
10.
\(JJ
05!C- Mo / V
lU
0
1-11
BORON HYDRIDES AND RELATED COMPOUNDS

[The basic principles of the structure and naming cf boron hydride cage compOUnds have
been discussed in Chapcet 16. See panicular!y Fig. 16.50. A very similar figure is presented
in the Red Book with a similar explanation. The names cf lhe structure types are summarized in Table 1-8).
Tablel-8
Summary ol palyfledral
palylnw......flydricle strvcturetypes, according to
st<Mchiametry and electron
counting r.calianships
closo-
Closed polyhedrul structure with triangular lllces only; known only as

with moleculur formula (8ftHn)1 - ; (n + I) skele!al electron-pairs for
polyhedron.
nidoNest-like, nonclosed polyhedral structure; molecular formula BftHft . .:
(n + 2) skeletal electron-pairs; n ve rtices of the parent (n + I)-atom
occupied.
"- .,..
aradmo- :.:, Web-like, ilonclosed polyhedral structure; molecular formula B,.Hft + 6 ;
electror:s>airs; n vertices of the parent (n + 2}-atom
..:
_ 3..
hypho,
occupted.
Net-like. nonclosed polyhedral structure; molecular formula BftHn + 1 ;

(n. + -4), skeletal
n vertices of !he par;nt (n + 3)-atom
l7(Coiton. F. A. J. Am.
$. 196&. SlO. 6230.(
Index
Absolute configuration of complexes, 495-496

Absolute electroneg:.tivity, 351
Absolute hardness. JSI
Absorption spectra of lomhanicle
and actinide ions. 604-607
Acceptor number (AN), 370
Achiral molecules, and point
groups. 64
Acids, 2
ha rd :and soft, 344-355
puameters of. 337
reaction rates influenced by.
SS3-SSS
cataly5ts. 378
sulfUric acid. J6.t-3b7
metal hy\lrides as,
643
Sec- ttlso Acid-base chemistry
a11d Base
Acid-base chemistry, 318-358
acid and base pnrnmeters. 337
bond energies. 340-341
concepts nnd definitions,
318-332
and elect ro negativity. 3S0-35S
generalized acid-base concept.
326-332
hard and soft acids and bases.
344-3S.S
measures of acid-base
strength. 330-344
A78-
proton Spoi!Jies. 342-l-43

solvation effects, and "anomalies," l-43-344
steric effects, 341-l-42
symbiosis. 348-350
Sec- also Acid and Base
Actinide dements, 28,
Affinities
electron, 40-43, 333-334, 339,
880-884
methyl cation, 353-354
proton. 330-333. 339, 3S3
Agosric Interaction, 693
Alkali halides, 308
Alkali metals, 27
Alkaline earth metals. 27
Alkane activation, 693-69S
Alkene complexes, 662-664
Alkene hydrogenation, S03,
706-708
Alkyl complexes, 655-657
Alkyne
662-666
Allen, L. C., 191
Allred-Rochow electronegativities, 190, 19S
Allyl complexes, 666-668
Alternation of electroneptivities,
884-885
A.luminum bromide, ZOS-206. 247
Arnines. basicity of, 329
Ammonia, 360-362
basicity of, 329

and chelate effect, 523
physicnl properties of, 361
solutions of metals in, 362-364
Ammonium tetrafluoroborate,
205
Anemia. 907
Allgular wnve functions, 14-17
Anions
carbonylate, as nucleophiles,
703-705
he.teropoly, 760-764
isopoly, 7SS-760
nucleophiles, 703-705
polyatomic zinll, 817
Anomalous ionization energies,
and electron nffinities,
880-884
Antibiotics, 954-955
Antibonding moleculnr orbital,
IS4
Antiferromagnetism, 467-468
Aprotic solvents, 369-373
Aqueous solvents, and nonaqueous solvents, 359-386
Arachno structures, 798-800, 807
Aragonite, 98, 953
Arene complexes, 681-683
Arrhenius acid-base definition,
319
Associative n:actions substitudon, S40
Index
Aslllline, 851-852
Asymmetric syntheses. 502-503
Atom
electronic structure of, 10-45
hydrogen, 10-20
polyelectronic, 20-43
sizes of. 33-35
Atomic inversion, 237-240
Atomic radii, 290-296
Atomic states. 26-27, A7-A I2
Atomization, 307
Aufbau principle, 23-26. 162
AurophUicity, 884
Axis of rotatory inversion, 77
Azotobuctrr vintlandii, 934
Back bonding, 393-394
Bailar twist, 556
Band theory, 270-272
Base, 2
hard and sofr, 344-JSS
parameters of, 337
reaction rates innucnced by,
553-555
solid C<ltalysts, 378
Su ufsu Acid and Acid-base
chemistry
Basicity, o( ammonia ami
amines, 329
Bednorz, J. G .. 285
Bent bonds, 2:30-231, 251
Bent's rule, 22S-229. 247
Be111man. R. G., 694
Bernal. I. .5311
Berry, R. S.. 241 -243
Berry pscudorutation. 2-10-243
Beryllium, 163
Belhe. H;tns, 394
Bgroup elements, 27-21!
Bijvoet analysis, 495
Biochemistry
o( iron. 935-941
or nonmeuls. 953-95-1
Biologicnl systems
essentiol ant.! trace elements in,
941-953
inorgnnic chemistry of,
889-964
Blue copper p roteins, 912-916
Bo<ly-centeret.l cubic
121
Boggsite, 2, 5, 7, 747
Bohr magnetons (BMl. 462
Boiling points, and chemical
forces. 307-310
Boltzmann distribution. 266. 272
Bond angles
and hybridization, 220-229
and nonbonded repulsions,
229- 231
and ..,. bonding. 203-2 I 1
Bond eneraies, A21-A34
Bonding
in coordination compounds,
387-433
and group theory, 71- 74
in noble gns fluorides, 829-831
Bonding molecular orbital. tS4
Bonding theory, 139
Bond lengths, 232-233. A21-A34
in chromium carbonyl complexes, 427
Bond multiplicity, 232-233
Boranes, 789-800
Borazines, 76S-769
Born exponent, 102-103
Bom-Habcr cycle. 108-114, 201,
288. 311, 340, 355, 357
Born-Landt equation, 103. 296.
312, 340. 408
Boron. 164-166
Boron cn.:e compount.ls, 789-807
Bratsch. S. G., 196. 1!53
Bravais Jauices, 7S. 76
Breslow. D. S.. 7I I
DrioJsing
JOS. 51:!. 6'!.7.
636
Bromine trinuori.Je. 209
Bro nste.J. J. N .. 318
Brtllnstet.I-Lowry acid-tr.tse definition.
Brown. H. C., 387
8-strain, 342
Buckyball, 82, 86
Cages, 738, 71!5- 71!9

Calcite, 98. 953
Caldernz.zo, F., 696
Calvert , R. B. , 692
Corbcne complexes, 6S5, 657-662
Carbide complexes, 6S5. 657-662
A-79
Carbon. 164-166, 861-863

Carbonylrue complexes, 639-641
as nucleophiles, 703-705
Carbonyl complexes, 630-649
brid11ina. 635-638
polynuclear, 633-639
preparation and properties of,
632-633
substitution reoctions in,
686-688
Carbonyl nuoride , 211-213
Carbonyl hydride complexes,
641-647
800-801
Carbyne complexes, 6SS,
657-662
Cotalysis. by or.:anometallic
compounds, 705-723
Catalysts
and asymmerric syntheses,
502-503
solid acid und base, 378
Que notion . 738-741
Cut ions
halogen. 8-47-848
polymomic zinll, 817
polyhalo.:en, 848
Center of symmetry. 48-49
Cesium chloride. 95-96
738-764
ChnrJcters. 6 1
Character tables. S9-63.
Al3-A:!O
Charge
in electro11!6
Char.:e tr.1nsfer spectra, 4SS-4S9
Chelate effect, S22-S31
Chelate rinas
conformation ol, 498-502
a nil Jahn-Teller effect, 454
Olelates, lanthanide, 610-613
Chelate therapy, 956-958
Che mical forces. 290-317
effects of. 307-314
types of. 296-300
Chemical reoclivily. 5-1
Chernick. C. l., 70
Chevrel phnses, 818
Chirol molecules, and point
64, 240, 502
A-&0
Index
Chloride acceptors nnd donors,

312
Chlorophyll, and photosynthetic
reaction center, 917-919
Chromium carbonyl complexes,
bond lengths in, 427
Circular dichroism (CO), 4%-499
Claasen, H. H., 70
Clathrate compounds, 304-306
Claahro-chelates. 530
Clays, 7SO
Clementi. E., 31, 32
Ooso structures, 798-800, 807
Clostridi11m pastt'ltriarltlm, 934
Clusters. 738. 807-819
Coenzyme. 919
Coenzymes, vitamin B 11
929-931
Collman's reagent. 704
Complex formation. of molten
snits, 377-378
Complex solids, 253-263
Concentration, and stability,
590-593
Conductivity
of coordination compounds.
389
in ionic solids. 266-269
in metals. 271 - 272
in semiconductors. 212-276
Conductors, one-dimensioll31,
752-755
Cone angles. 688-689. 690
Conformation of che late rings.
498-502
Conjugates. 319
Corliuncto structures, 798-800
Conven;ion factors and units.
AJ-A6
Coordinated ligands. nucleophilic

and elecrrophilic auack of.
700-703
Coordination complexes
asymmetric syntheses, catalyzed by. 502-503
bonding. 391-433
conductivity of, 389
electronic spectra or. 433-459
of inner transition metals,
608-613
magnetic properties of.

459-468
pi bonding in, 421-433
reactions. kinetics. mechanisms. 537-576
structure. 472-536
Coordination isomerism. 521-522
Coordination number I, 472-473
Coordination number 2, 473
Coordination number 3, 474
Coordination number 4, 474-479
Coordination number S, 479-488
Coordination number 6. 488-503
Coordination number 7. 503-507
Coordination number 8, S07- 509
Coordination numbers
generalizations about, 511-5 13
higher, 509-5 II
and radius ratio, 123. 473
Corrin ring, 929
Conon effect. 496, 497, 498
Coulomb's law, 100
Coulson, C. A., 140
Covalent bonds, 138-202, 296
and ionic bonds, 129-134,
258-260, 678-680
and reactions of molecules.
237-246
solids held together by.
UB- 276
Covalent energy, 340
Covalent radii, 291-296
Craig/Paddock model, 773
Cristobalite. 97-98
Crown ethers, 525
Cryptates. 530
Crystal field (CF) theory. 391.
394-413, 474
Crystal field stabilization energy
(CFSE), 399-401.408-413
Crystal lattices, and efficiency of
packing, 118-122
Crystallography. 74- 85
Crystals. imperfections in.
263-265
Crystal systems, 75
Cubic closest packed (ccp)
system. 120
Cubic crystal system. 7S. 78
Curie's law, 466
Curie-Weiss law, 467

Cyclobutadiene complexes,
684-686
Cycloheptatriene complexes,
683-684
Cycloocratetraene complexes,
684-686
Cyclopentadienyl complexes
reactions of, 700-703
structures of, 673-678
synthesis of, 680-68 I
Cytochromes, 569-572, 891-895
d block elements, 27-28, 583-588
Defect semiconductors, 274-276
Degenerate, representations, 62
Delocalization, 143
Density of states (OOS), 280
Oeoxyhemerythrin, 909
Deoxyribonucleic acid (DNA),
958-960
Descriptive chemistry, of metals,
571-6rl.
Dewar, M. J. S., 772
Diamagnetic atoms, 22
Diamagnetic susceptibilities.
462-463
Diamagnetism, 467-468
Dichloroiodate anion, 209
Diffraction
neutron, 235, 238, 497, 64S
X-ray. 233-235, 238, 497. 64S
Dihydrogen complexes. 644-646
Dimension of representations. 61
Dinitrogen complexes. 566,
653-655, 933-93S
Dinuclear complexes, 808-813
Dioxygen
binding, transport, use,
895-910
and heme, 895-897
and myoglobin, 897-899, 900
Dipole-dipole int.eractions, 298.
307
Dipole moments, 64-65, 201
Disorder, crystallographic, 80-85
Displacement, nucleophilic,
243-244
Dissociative substitution reactions, 540
l11dea
Distortions, from perfect octasymmetry, 488-489

Donor number (ON), 370
Orngo, R. S., 218, 233 n, 323.
335,336,337,341, 3S2
Dull, N . K., 556
Duval, C . 514
Eigenfunction, 10
rule, 624-{)30
Electrochemistry
of halogens and
pseudohalogens. 853
in nonaqueous solutions.
381-382
Electrode potentials, 378-383,
A35-A37
Electron
countiD& complexes, 625-630
Electron affinities, 40-43
anomalous. 880-884
Ekctron configuration, 23
Electronegativity, 142, 171.
182-199, 2S8
Allred-Rochow. 195
alternation of. 884-885
of clements, 187-190
198-199, 258
aroup.
and hardness and softness of
acids and bases. 35C)..355
183-258
Pauling's electronegntivity.
193- 194
recent advances in theory for ,
186- 191
variation of. 191-193
Electroneutrnlity principle.
39l-394
Eleclronically equivalent groups,
647
Electronic spectra
of complexes, 433-459
of lanthamide and actinide
Electron-nucleus attraction. 27
Eledron parnmagnct.ic resonance
(EPR). 4 14. 914
Eleclron spin. and Pauli pri,...
ciple, 21-23
Electron transfer. and respirat ion

and photosynthesis, 911 -919
Electrophilic allnck of coordinated ligands, 700-703
Electrophilic substitution in
square planar complexes,
538
Elements
and atomic radii and multiple
bonding parameters. 292
electron affinities of. 42-43
electron configurations of,
24-ZS
electronegativities of, 187-190
essential and trace. in biological systems, 941 -95)
ionic radii of. 105-108
ionization energies of. 35-38
nuclear charges of, )4
periodicity of, 27-29
potassium-zinc comparison by
electron confic:urotion,
582-587
slllndord reduction poten.tials
of. A35-A37
E limination and insertion reactions. 695-700
Elion. G. B.. 929
Enantiomers. 476-4n. 495
Energetics of hybridization.
225-229
Energy
bond, 34C)..341. A21-A34
bond lengths ant.l ionization
166-167
crystal ficlt.l stabilization
(CFSE), 399-401
exchange, 27, 141
ionization. 35- 38, 579
la.ttice, 99-11 S
of orilitals. 18-20
sources of, for life, 889-891
Enthalpy, 312
Entropy. 311
Enzymes. 919-932
Escher, M. C., 90
Essential elements, in biol08ical
systems. 941-953
E.thylenediarnine complexes. and
chelate effect, 523
A-81
Eutrophication. 3
Exchange ene.rgy. 27. 141
Excited state outer sphere electron transfer reactions,
561 - 565
Excited lerms. 441 , Al2
Experimental determination, of
molecular structure. 233-237
Experimental evidence for.,.
bonding, 425-433
Extended X-ray absorption fine
structure (EXAFSJ. 238, 639
Eyring. Henry, 391
Facial isomer. 491-492
Faja ns, K . 129
Fajans' rules. 129-130. 169, 258.
309
Faraday. Michael, 460
Faraday method ror magnetic
susceptibility, 461-462
/block elements. 28, S99-613
Fermi level, 271
Ferredoxins. 911-912
Ferroma,netism. 467-468
Firsl-stnge interclates. 751
Fischer corbenes. 658
Fischer. E. 0 .. 669
Fischer- Hafner adapcalion , of
Friedei- Crafts reaction. 681
Fischer- Tropsch reaction. 711,
7 17
Fixmion. nitrogen. 933-935
Floot.l. H .. 319
Fluwchun. ant.l point symmetry,
57-58
Auorides. or noble eases.
821!-831
Fluorine, 163- 164. 849-851
chemistry,
843-845
Fluorite, 97, 288
Fool's gold. 2
f orbitals. 604
Formal
146-148
F ree radical mechanisms.
244-246. 963
Frenkel defecl , 265. 266
Friedei-Crafls reaction, 681
F-strain, 341-342
A-82
111d
' G.'lsotine. synthetic, 715-717

Gns-phase proton nffinities.
332-333
Geometric iso merism. in OCID
hedrol complexes. 491-492
Gerade orbitals. 17-18
Gerade symmetry. 48, 160
Gillespie. R. J .. 832
Glide plane, 77
Gold, 2. 881-885
Gouy mechod for magnetic susceptibili ty. 461
Graham. W. A. G .. 694
Grignnrd reagent. 680, 681 , 704
Grou nd stale. 23
Ground terms. 441, Al2
Group electronegativity, 196-197,
202
Group l A (I). 593-594
Group 18 (I I ), 597-598
Group IIA (2), 594
Group 118 ( 12). S9&-S99
Group 1118 (3) . S94
Group IVB (4), 594
Group VB (51. S94-S9S
Group Vl8 (61. S9S-596
Group VIJB (7) .596
Group{s) VIIIB (8. 9. 10),
S%-597
Groups (symmetries). and character tables. AI3-A20
Group theory, and symmetry.
4<>-91
Gu.:s1 molecules. 3()5
Gucgcnberser. L. J .. 223. 24 1
Gutmann, V ., 323
Half-lives. of selected actinide
nuclides, 614
Halides. 308. 309, 848-852
Halogen cations, 847-848
Halogen oxides, 8Ml-847
Halogens, 824
electrochemistry of. 853
heavier. oxyacids
physical inorganic chemistry
or, 848
in po5itive oxidation states,
837-848
and pseudohalogens, 852-853
or.
Hapticity, 629. A71

Hard acids and bases. 344-355
Hard-soft acid- base (HSAB)
interaction, JSI
Hartree-Fock method, 20
Heavier tronsition metals,
587- 588
Heck, R. F., 711
Heme, and dioxygen, 895-897
Hemerythrin, 908
Hemoglobin
physiology or, 900-902
structure of, 902- 908
Hermann- Mauguin system,
71, 78
Hess's law, 108
Heteroboranes, structure prediction for, 802-807
Heterocatenation, 741-742
Heterocyclic inorganic ring
systems, 775-780
Heterogeneous catalysts, 70S
Heteronuclear diatomic molecules. molecular orbitals in,
167-175
Hetenopoly anions, 760-764
Hexagonal crystal system. 75. 78
Hexanuclear clusters, 816
Hexgonal closest packed (hcp)
SYstem, 120
Hieber, Walter. 643
Highest occupied molecular
orbital (HOMO), 35 1,428.
721,722
High-temperature superconductors, 285- 288
Hinckley, C. C., 61 3
Hoffman, R. 387, 647
Homocyclic inorganic syste ms,
780-785
Homogeneous ca talysts. 70S
Homonuclear diatomic mole
cutes, molecular orbitals in,
160-166
symmet ry,
Horizontal plane
Sl
Host molecules. 305
Hoyano. J. K., 694
Hilckel rule, 712
Hund's rule, 26-27
or
Hybridit.ation, 14&- ISJ

energelics of, 225-229
and overlap. 153
and st ructure, 220-231
Hydrates, 304-306
Hydration enthalpy, 312
Hydride complexes , 641-644
Hydroformylation, 711-712
Hydrogenation of alkenes , .503,
706-708
Hydrogen atom, 10-20
Hydrogen bonding. 300-306
Hydrogen-bridged systems, 305,
316. 646, 79 1
Hydrogen migration, 709
Hydrolysis constants, and
charge-size functions. 328
Hydrometallurgy, 382-383, 384
Hydron. and proton, 318, A49
Hypho structures, 798-800, A71
Identity operation, 51
lmmobilit.ed homogeneous catalysts, 718
Imperfections. in crystals.
263-265
Improper rotation, S2-S3
Impurity semiconductors,
274-276
Induced dipole interactions,
298-29')
Inert complexes, S41-S48
Inert pair effect. 877-879
Infinite metal chains, 818-819,
820
Infrared (IR) spectroscopy.
65-71. 235, 238
of carbonyl complexes,
428-431, 633-634
Inherent atom electronegalivity,
186
Inhibition. and poisoning,
925-929
Inner sphere mechanisms,
S65-S61
Inner trnnsilion elements, 29,
599-613
Inorganic chains. 738-764
Inorganic
14
lnd
ll'lOI"g:lnic chemistry
of biologicnl systems, 889-964
introduced, 1-9
IUPAC nomenclature of,
A46-A77
literature of, AI-A2
lnserrion and elimination reactions, 69.5-700
Instantaneous dipole-induced
dipole interactions, 299
460
Intensity of
l ntercalatioo chemistry, 750-752
l nterchanae associative substitu
tion reactions, S40
lnterchanae dissociative substitution reactions, S40
lnterhalogen compounds.
837-839
l ntemationol system of symmetry, 77, 78
International System of Units
(SI), A3-A6
l ntenmtional Union of Pure and
Applied Chemistry (IUPAC),
A46-A77
Internuclear distances. and
atomic radii. 290-296
lnterstitialcy mechanism, 266
Interstitial mechanism, 266
Intrinsic semiconductors.
272-274
Inversion. atomic. 237-240
Inversion cemer. 48-49
In vitro nitrogen fixation.
933- 934
In vivo nitroen fixntion. 934-935
Jo n-cyclotron resonance spectroscopy, 331
Jon-dipole forces, 297
Ionic bond, 92-99. 129-134,
258-260.296-297,678-680
Ionic charae, 146
Ionic compounds, 92-137
thermodynamic calculations
for, 127-129
Ionic radii, 105-108. 291
Ionic resonance ene.rgy, 194, 201,
340
solids. conductivity in,
266-269
38-40
loniruion energy. 35-38
Ionization isomerism. 521
lon migration. 266-269
Ions. 92
bond lengths and
eneraies, 166-167
polyatomic. 117
polyholide, 839-843
size effects. IIS-127
Iron, biochemistry of, 935-\141
Irreducible representations, and
character tables, 59-63
Irving-Williams series, 348-349,
4S4
Island model of phosphazenes .
772
lsoelectronic complexes, 640
lsolobal fragmc:nts, 647-649
Isomerism, 415-417. 486-488
in five-coordinate complexes.
486--488
geometric. 461-462
linkage isomerism. 5ll-521
opti<:nl. -192-494
types of. 521-522
Isomerization. and mcemization.
5SS-S51
lsopoly anions. 155-160
lsostructurnl carilonyl complexes. f>.IO
1-strain. 342
A-83
Labile complexes, S41-S48

Lacunary struct ures, 762
Lan&ford. C. H., SS3
lanthanide chelntes,
Lanthanide elements, 28,
599-607, 609-610
laporte rule, and transitions. 438
latimer diagram, 588. 853
lattice energy. 99-11 S
lattice points, 74
Lllttices. and efficiency of packing, 118-122
Layered structures, 260-262
lecompte, J .. Sl4
lewis. G. N .. 324-325
lewis acid-base interactions.
systematics of. 336-340
lewis acid-base definition.
324-325
Lewis structu re, 138-139
life. enciJY sources for, 889-891
l..ianntl cone angles, 688-689. 690
ligand field effects, and reaction
ru les, 5S0-551
l ignncJ field (LF) theory. 391.
434
LignncJ field stabili.zation energy
ILFSEl. 47-1, 578
LiC;Jnd aroup orilitals (LGOs).
17.5-176. 179-182. 414-418.
421.
l.igand iS\lmerism, S21
Licnmls
Jalfo!. H. H .. HIJ, 1115. 258
Jnhn. H. A. "-l'.l
Jnhn-Teller theorem. 403.
449-ISS. 524
Janowicz. A. H .. 694
Jlkgensen. Sophus Mads. 387
Kinetics
of octahedral substitution,
548-551
of redox reactions. 551-512
of square planar substitution.
S38-S41
IGneJic stability, S41-S48
KoopnlllllS' theorem, 39. 166,
351
untl .:lcctron counting. 626

ond
effect. 413
nucleophilic and electrophilic
all:rck of, 700-703
scpulchrute, 530
Lia;und-to-metal ch;lfge transfer
(LMC11. 457
Linear combination of atomic or(LCAO) method, ISJ
linkage isomerism. 513-521
Lipscomb, W.. 387
literature of inorganic chemislry. AI-A2
lithium. 163
143
london dispersion forces, 299.
307, 310, 314. Su also
A-84
Index
Loodon dispe.rsion forces

van der Waals forces and
van der Waals. radii
Lowest unoccupied molecular orbital (LUMO), 351, 721. 722
Low oxidation state transition
metals. 580-581
Lowry, T. M. 318
H . 319
acid-base definition,
319- 320
Macrocycles. 52S- S31
Madelung constants. IOQ-101,
199. 262-263. 295, 308, 311.
340
Madelung energy, 199, 291 , 311,
340
Magnetic properties
of complexes, 45. 459-468. 485
of lanthanides and actinides.
607
Magnetic quantum number. 19
Mngnetic susceptibility
mass. 466-463
molar. 461
volume, 460
Maim. J. G. 70
Map of twist angles. 490
Marcus theory, 571
Mass spectrometry. 239
Maximum multiplicity, 26-27
Mechanisms
inner sphere. 565-567
outer sphere. 558-561
of redox reactions. 557-572
of substitution reactions.
545-547, 551-553
Medicinal chemistry, 954-960
Meissner effect. 285
Melting points. and chemical
forces. 307-310
Metal alkyl complexes. 65.5-657
Metal carbonyl complexes,
630-649
Metal chains. infinite. 81S-819,
820
Metal clusters, 807-819
Metal complexes, as probes of
__
acids_, 95S-_960
.-'-'-- - -
Metal ions, and nepbelauxetic

effect, 413
Metallac.vbornnes. 801-802
Metallocenes, 669-686
Metalloporphyrins, and respiration, 891-895
Metallothioneins, 932
Metals, 27-28
descriptive chemistry of,
577..()22
general periodic trends,
578- 579
heavier transition, 587-588
inner transition, 608-(,09
oxidation states of, 58(}...581
solutions of, 377
solutions of. ammonia. 362-364
Metal-to-ligand charge transfer
(MLCT), 457
Methyl migration, 696-698
Migration, ion, 2M-2tf)
Minerals, silicate, 742-750
Mirror plane, 48
Mixed valence complexes.
568-569
Mobil gasoline synthesis, 7 II.
717
Models, pnper, A4(}...A43
Molar susceptibility, 461
Molecular orbital (MO) theory.
!39, 153-182, 413-433
and Tr bonding, 420-425
and eighteen-electron rule,
624-625
and molecular structure.
218-220
Molecular orbitals
in heteronuclear diatomic molecules, 167-175
in ltomonuclear diatomic molecules, 16(}...166
of metallocenes, 670..()73
in octahedral complexes,
414-418
in square planar complexes,
418-420
symmetry of, 160
in tetrahedral complexes.
418-420
in triatomic molecules and
ioos, 175-182
Molecular structure
experimental determination of,
233-237
and hybridizatioo, 22(}...231
and molecular orbitals,
218-220
Molecular symmetry, and point
groups , 53-59
Molecules
reactivity of, 203
stereochemicnlly nonrigid,
723-730
structure of, 203-220
Molten salts. 374-378
Monoclinic crystal system, 75. 78
Monsanto acetic acid process,
712-714
Morris. 0 . F. C., 312
Mossbauerspectrascopy, 908,
909
Muetterties, E. L., 223, 241
MOller, K. A ., 285
dectronegativities, 183-186. 258
Mulliken labels, 61
Multiplicity, 26-27
Myoglobin
and dioxygen. 897-899, 900
physiology of. 900-902
Naples yellow. 458
Natta. G . 718
Negative oxidation state, S80-581
Neon. 163-164
Nephelauxetic effect. 413
Neutral utom electroneg;llivity.
186
Neutron diffraction, 235, 238,
497.645
Nido structures. 798-800, 807
Nitrite ion, 175-182, 201-202.
210, 249
Nitrogen. 164-166, 864-865
Nitrogen dioxide, 210
Nitrogen fixation, 933-935
Nitrosyl complexes. 650..()53
Nilryl ion. 210
Noack, K., 696
Nobel prize winners
Bednon, J. G., 285
Brown, H . C., 387
Index
Nobel priu winners (Continued)

Elion. G . B., 929
Fische.r. E . 0 . 669
Hoffmann, R., 387, 647
Lipscomb. W .. 387
Miil!er, K. A., 285
Natla, G., 718
Taube, H . 387
Werner, A., 387
Wilkinson. G . 387, 669
Ziegler, K., 718
Noble gases. 357,824, 825-836
discovery and early chemistry,
825-827
fluorides, 828-829
Nomenclature of inorganic chemistry. A46-A77
Nonaqueous solvems, 359.
360-373. 381-383
Nonaromatic alkene complexes,
662-668
Nonbonded repulsions, and
structure, 229-230
Nonbonding orbitals, 157
Nonmetals, 28
biochemistry of. 953-954
and d orbitals, 866-875
hybrid orbitals for, 19.5-196
periodic anomalies of, 876
Nonphotosynthetic pl'ocesses.
889-891
Nonrigid molecules. 72>-730
Normalizing constant, 156
Nuclear magnetic resonance
spectroscopy. 7. 8.
239. 335. 469, 471
of dihydrogen complexes.
645-646
of fluctional molecules,
725-730
of hydride complexes, 644
of polyoxymetallates, 762-764
shift reagents, 613
and water exchange reactions,
549-550
Nucleic acids
metal complexes as probes of,
958-960
reactiun of cisplatin with, 957
Nucleophiles, carbonylate anions
as. 703-705
Nucleophilic attack of coordinated ligands. 700-703

Nucleophilic displacement.
243-244
Nucleophilic substitution
in octahedral complexes,
548-556
in square planar complexes.
540-547
Oak Ridge Thermal Ellipsoid

Program (ORTEP) diagram,
234-235, 478
Octahedral complexes, 397-399,
414-418,441,448-455,
488-489
geometric isomerism in,
491-492
optical isomerism in, 492-494
Octahedral substitution, kinetics
of. 548-557
Olivine, 253, 256
One-dimensional conductors.
752-755
Optical activity, 63-74, 492-494,
697-698
Optical rotatory dispersion
(ORO), 496, 497. 498
Orbitals
and atomic structure, II
d. 395-396
d, in "' bonding, 868-875
energies of. 18-20
/. 604
lil)and group (LGOs), 17.5-176.
179-182. 414-420
of metallocenes, 670-673
molecular. Su Molecular
orbitals
p in "' bonding, 861-866
symmetry of, 17-18, 160
Organometallic chemistry, 7,
623-737
Organometallic clusters, struc
ture prediction for, 802-807
Organometallic complexes
catalysis by. 70.5-723
reactions of, 686-705
Organomet<JIIics, 623
Orgel diagrams, 440, 448
A-85
Orthorhombic crystal system, 75,
78
Outer sphere mechanisms.
558-561
Overlap
and hybridiullion, 153
and symmetry, 157- 160
Oxidation. 2
Oxidation states
comparison of properties by,
581-582
and emfs, 588-599
of halogens. 837-848
of inner transition metals,
599-602
range of, 581
stabilities of, 588-590
of transition metals, 580-582
Oxidative addition, and reductive
elimination. 538. 689-695
Oxide acceptor. 320
Oxides
acidity of nonmetal. 327
acidity parameters for. 321
basicity of melnl. 326-327
halogen. 846-847
phosphine. 868-871
Oxo process, 711
Oxyacids, of heavier halogens,
845-846
Oxyfluorides.846-847
Oxygen. 163. 843-84.5
1'<1cking. aml crystal lattices.
118-122
Paper models. A40-A43
Paramagnetic atoms, 22
Paramagnetism, 460-468
Pauli exclusion principle, 2'2
Pauling, Linus. 139, 182, 183,
185. 193-194, 391. 811
Pauli pl'inciple, 21-23
Pauli repulsive forces, 22. 206
p block elements, 28
Pearson, R. G., 352
Peattie, Donald Culross, 960
Penetration, 14
Pentadienyl complexes, 666-668
Pentafluorotellurate anion, 209
Periodicity, 857-888
diagonal relationship, 860-861
A-86
Index
Periodicity (Contimtetf)
of elements. 27-29
first- and second-row anomalies, 858-861
fundamental trends, 857-858
size effects in nonmetals.
859-860
of translawrencium elements.
6 15-617
Perovskile, 253, 285
Perutz mechanism. 903
pH , and solvents, 322
Phorphorus pentafluoride, 205
Phosaene, 205
Phosphazene polymers, 773-775
Phosphazenes. 769-773
Phosphine complexes, and
oxides. 871
Phosphorus, and nitrogen,
1164-865
Phosphorus oxyfluoride. 205
Phosphorus trihaJides, 211
Photodehydrogenated catalyst,
718-723
Photoeleclron spectroscopy, 16.5.
431-433
Photoexci ted semiconductors.
272- 274
.
Photosynthesis, 916-917
and chlorophyO, 917-9t9
electron transfer. and respiration. 911-919
Physiology. of myoglobin ond

hemoglobin. 900-902
Pi bonding, 4:!o-433, 872
in coordination compounds,
421-433
d oroi lals in, 868-875
p orbilals in. 861-866
Platinum anticancer drugs, 559,
951
Platinum pop, 718-723
Point groups and molecular symmetry, SJ-59
Point symmetry, 48
Poisoning, and enzyme inhibi-
tion, 925-929
Polar bonds, solid-state materials
with. 276-288
Polarizability tensor, 67
Polarization of ions, 129-134
Polilzer, P. 849
Polyatomic zintl anions and
cations. 817
Polyelectronic atom, 20-43
Polyholide ions. 839-843
Polyhologen cations, 848
Polymers, and phosphazene
polymers, 773-775
Polynuclear carbonyl complexes,
633-639
Porterfield, W. W., 295
Positive oxidation states.
halogens in, 837-848
Posuransition metals, 28. 876
Potassium, 309, 582- 587
Potentials, electrode, 378-383
Pourbaix diagram, 591- 592
Praseo complex. 388, 491 , 493
Predominance area diaafam, 591
Prewitt, C. T ., 116-117
Principal axis, 51
Prism, trigonal prism, 489-491
Probability function, 13
Prosthetic grou p, 919
Proteins. and blue copper proteins, 912- 916
Proton
affinities, 332- 333
and hydron, 318, A49
Protonic solvents, summary of.
367- 369
Proton sponges, 342- 343
Prussian blue, and linkage isomerism, 519-521
Pseudohalogens, 852-1153
Pseudorotation, 240-243
Racah parameters, 443
Race.rnizalion, and isomerizat ion,
555-551
Radial wave function (R), I 1-1 4
Radii
atomic, 290-296
covalent, 291-296
iooic, 114-117, 291
of potyatomic ions, 117
thermochernicals, 117
van der Waals, 290-291, 301,
720
Radius ratios, and coordination
number, 123, 473
Radon, 836
Raimondi. D. L., 31, 32
Raman spectroscopy, 65-71,235,
239
Rate law, for nucleophilic substitution, 54()-543
RAy. P. C . 556
Rfly-Outt twist. 556
Rayleigh, Lord, 825
Reaction rates
innuenced by acid and base.
553-555
and ligand fteld effects.
550-551
Reactions
of coordination compounds,
537- 538
excited srate outer sphere electron transfer, 561-565
of organometnllic complexes,
686-705
redox. Su Redox reactions
watu-gas shift, 710
Reactivity, 5-1
and d orbitals. 875-876
of molecules, 203
Redox reactions
in biological systems, 569-572,
891-895
mechanisms or. 557-572
Reducible representations, 62-<.3
Reduction, 2
Reduction potentials of elements.
A35-A37
Reductive elimination, and
oxidative addition, 689-695
Relativistic effects, 579, 879-880
Repulsive forces. 102. 229-230,
291, 299-300
Resonance, 141 , 142-146,340
Respiration
electron transfer, and photosynthesis, 911 -919
and metalloporphyrins,
891-895
Ribonucleic acid (RNA), 958-960
Ri11&S, 738, 76.5-785
Room-temperature molten salts,
375-376
Rotational axis, 9-5 1
Rube Goldbea-g effect, 903
Index
Rubredoxins, 911-912
Rutile, 97
Salts
molten, 374-378
zin1l. 527
Sanderson, R. T . 190. 19.5, 198
s block elemeniS, 27
Scanning IUnneling microscopy
(STM), 4
Schoenflies system, 77. 78
Schottky defect, 263. 26.5
Schouky-Wagner defect, 263,
26.5
Schrock carbenes, 659
Schrodinger equation. 10. 20
Screening constant, 31
Selection rules for electronic
transitions, 437-438
Self-consistent f.eld (SCF), 20
Semantics. and the periodic
table. 29-30
Semibridging ligands, 636
Semiconductors
impurity and defect, 274-276
intrinsic and photoexcited,
272-274
Seppelt, K.. 866
Sepulchrate ligands .530
Shannon, R . 116-117
Shapley, J . R . 692
Shibata, Y. .514
Shielding, 30-33
Sickle ct!ll
CSCA). 9tl7
Silicote minerals. 742-7.50
Silicon, and carbon, 861-863
Silver halides. 309
Sixteen-electron rule, 625
Slater. J. C., 31. 32. 140
Slipped ring complexes. 677
Sodium chloride. 94-9.5
Soft acids and bases, 344-3.5.5
Solid catalysts, acid and base, 378
Solids
complex, 253-263
held together by covalent
bonding, 269-276
Solid-stale materials. with polar
bonds. 276-288
Solid superacids, 378
Solubility, 310-314
Solutions
of metals, 377
of metals in ammonia, 362-364
in molten sa! IS, 374-378
Solvate isomerism .521
Solvents
aprotic, 367- 369
aqueous and nonaqueous,
3.59-386
molten sail, 374-378
and pH, 322
protonic. 367-369
Solvent system acid-base definition, 320-324
South African Synthetic Oil Limited (SASOL), 717
Space group. 78
Spectrochemical series, 405
Spectroscopy, 7, 8, 6.5-71. 16.5,
23.5, 238. :!39, 331. 428,
431-433
sp hybrid, 1.50-153
Spinels, 411-412
Spin quantum number, 21-23
Square planar complexes.
403-404. 418-eo. 4n-419,
.538-.547
Square pyramidal (SP) complexes, 480-482. 484-48.5
Stability
and concenlmtion. .59<1-.593
or oxidalion slates. 5118-590
lhermodynumic and kino:1ic.
.547-.54!!
Stablo:
.547-54!!
Stahle oxil.lation slates. 599-607
reduction pOtentials of
elements, A3.5-A37
States. density of. 280
Stereochemically nonrigid molecules. 723-730
Stereochemical models, A40-A4S
Stereoselectivity, and conformation or chelate rings. 498-.502
Stereoviews, A44-A45
Stuic effects. 229-231, 341-343,
.513, .516-518
A40-A45
Stem, K. H., 133
Structural techniques, time scales
for, 238-239, 724
A-87
Structure
of complex solids, 253-263
of coordination compaunds,
472-536
of cyclopentadienyl compounds, 673-678
and function in enzymes,
919-924
and function in hemoglobin.
902-908
and hybridization, 220-231
layered. 260-262
of molecules. 203-220
of molecules with lone electron
pairs, 206-217
and nonbonded repulsions.
229-230
prediction for heteroboranes
and organometallic clusters,
802-807
Subhalogen, 850
Subnodal maxima, 14
Substitution reactions
in carbonyl complexes.
686-688
in oclahedrol complexes
548-557
in square planar complexes.
538-547
Sugano. S .. 443-447, A38-A39
Sulfur hexafluoride. 205
Sulfuric acid. 364-367
Sulfur tetrafluoride. 208-209
Superadds. 378
Superconl.luctors. hightempt!rature . 2115-21!8
Superhnlogen, 850
Supersonic lranpart (SSf), 244
Swaddle, T. W., 553
Symbiosis, 348-3.50, 518-519
Symmetric hydrogen bonding,
302
Symmetry
and group Jheory, 46-91
of molecular orbitals. 160
octnhedraJ, 397-399, 488-489
anl.l opticnl activity, 63-74
of orbitals, 17-18
and overlap. 157-160
tetragonal. 403-404
tetrahedral, 401-403, 418-420
A-88
IIICI
Symmetry
74
Symmetry allowed transitions,
64-65
Symmetry elemems. 46-53
Symmetry forbidden IJ'ansitions.
64-6S
Symmetry groups, 53, A 13-A22
Symmetry operations, 46-53
Synthesis gas, 709-711
Synthetic gasol ine, 7 15-717
SysteiTI:ltic absences, 79
Talc, 7SO
Tanabe. Y .. 443-447, A38-A39
diagrams.
443-447, A38-A39
Taube, H., 387
Teller, E . 449
Term symbol.s . 'lh-27, A7-AI2
Tetrachloroiod ate anion, 209
Tetragonal crystal system. 1S, 18
Tetrn&onal symmetry. 403-404
Tetrahedral co mplexes. 401-403,
418-420. 441. 448-4SS,
474-4n
Tetranuclear clu sters, 815-816
Thermal ellipsoids. 234. n4
Thennochemical calcu latio ns,
predictive power of, 127-129
Thermochemical rddii, 117
Thermodynamics. and chelnte
effect. S"..J
Thermodynamic convention. 379
TherlllOOynumic stability.
S47-S48
Time scales for structural techniques, 238-239, 724
Tolman catalytic loops. 108
Toxicity, of biological elements,
1143-948
Trace elements. in biological
systems, 94 1-953
Transactinide e lements. 599-607.
613-617
T rans effect, S43-S4S
Transferrins, 937
Transition metal hydrides. acidities of. 643
Trnnsition metals, 27-28

heavy, 587- 588
nnd inner transition, 60S-609
oxidation states of, 580-582
Transitions, and Laporte rule.
438-440
Translational symmetry, 74
Trnnslawrencium elements. periodicity of. 6 1S-617
Transport, dioxygen , 895-910
Triatomic molecules and io ns.
molecular orbitals in,
175-182
Triclinic crystal system, 7S, 18
Trigonal bipyramidal (TBP)
structure, 480-483
T rigonal crystal system, 7S, 78
Trigonal hybrid, IS0-153
Trigonal prism, 4&9-491
Trimethylborane, 20S
Trinegative ions, 332- 333
T rinuclear clusters, 813-815
Tropylium complexes, 683-Q4
Tutankharnen, 458
Twist angles, 490
Ultraviolet (UV) radiation, 244
Ungerade symmetry, 4&, 160
Ungerade orbilnls, 17- 18, 160,
438
Uninegative ions, 332-333
Unit cell, 74
Units and conversion factors,
A3-A6
UnSQid's theorem, 19
Unstable complexes, S47- S48
Unsymmetric hyd rogen bonding,
302
Usnnovich, M., 325
Usanovich acid-base definilion,
325-326
Vacancy mechanism, 266
Valence bond (VB) theory,
139-153, 391-394. 474
Valence shell electron pair repulsion (VSEPR) model,
203-206, 217- 218
Valence state, promotion to,

148-149
Valence state values, 191
van der Waals forces, 2S2, 299.
Su also London disperson
forces
van der Waals radii. 2%-291.
301, 720.
also Londo n
disperson forces
Van Vleck, J. H 39S
Vaska's complex , 691
Vertical plane of symmetry, 51
"V ibrational Spectra and
Structure of Xenon TeiJ'afluoridc," 70
Vibronic transit.i ons, 438
Violeo complex, 388. 491. 493
Vitamin 8 12, and coenzymes.
929-931
Volumes of activation, 542, 553
Wacku process, 114-115
Wade's rules. 798, 80S
Walden inversion, 243
Walsh diagrams, 218
Water, physical pro perties of,
360
Water-gas shift reaction, 710
Werner, Alfred, 387, 388. 389.
390, 491, 49S
Wilkinson, 0 .. 387, 669
Wilkinson's catalyst , 707
Wuru.ite, %-97
Xenon,5. 70, 832- 836
X-ray diffraction, 233-23S, 2311,
497, 645
p-Xylene, 5-6
Ya tsimirskii, K . B., 117
Zeolites, 3-5, 7, 378, 715,
745-748
Ziegler . K., 718
Ziegler- Natta catalysis. 718
Zinc, S82-S87
Zinc blcnde. 96-97
Zinll salts. 527, 817
ZSM-S, 747-748
THE NAMES, SYMBOLS,

TOMIC Nt.t.lBERS, AND ATOMIC WEIGHTS OF TME ELEMENTS
a,.
Actinium
.luminum
Americium
.n1imony
Araon
.rsenic
Astllllne
arium
Barkelium
'eryllium
"oron
dromine
-udmium
..:alcium
-alifomium
_arbon
":erium
.:esium
r hlorine
_hromium
t:obalt
; opper (cupntml
t:urium
Ein'ltetnium
rbium
Europium
erm1um
r:tuorine
rancium
Gadolinium
allium
_._
Atomic
Symbol
Ac
AI
Am
Sb
Ar
As
At
Ba
Bk
Be
Bi
8
Br
Cd
Ca
cr
c
Ce
Cs
Cr
Co
Cu
Cm
Oy
Es
E.r
Eu
Fm
F
Fr
Gd
Ga
Atomic
weight
Nome
Symbol
89
(227)
13
:!6.981539
(243)
121.757
39.948
74.92159
(210)
137.321
(247)
9.012182
2n8.98037
10.811
79.904
112.411
40.078
(2SI)
12.011
140. 115
132.90S43
35.4527
51.9961
58.93320
63.546
(247)
162.50
Germanium
Gold (oumm)
Hafnium
Helium
Holmium
Hydroaen
Indium
Iodine
Iridium
Iron (frrrum)
Krypton
Lanlhanum
Lawrencium
Lead (plumbum)
Lithium
Lutetium
Maanesium
MalllJllnese
Mendelevium
Mm:ury
Molybdenum
Neodymium
Neon
Ge
Au
Hf
He
Ho
9S
51
18
33
8S
56
97
4
83
35
48
20
98
6
58
ss
17
24
27
29
96
66
99
68
63
100
9
81
64
31
167.26
151.965
(2S7)
18.9984032
(223)
157.25
69.723
Nickef
Niobium
NitrOgen
Nobilium"
Osmium
Ollyaen
PaDadium
Phosphorus
Platinum
In
I
lr
Fe
Kr
La
Lr
Pb
Li
Lu
Ma
Mn
Md
Ha
Mo
Nd
Ne
Np
Ni
Nb
N
No
Os
0
Pd
p
Pt
Atomic
Atomic
'*""-
w.tf;Jrt
32
79
72
2
67
I
49
S3
77
26
36
57
103
82
3
71
12
2S
101
80
42
60
10
93
41
7
102
76
8
46
IS
78
n.61
196.96654
178.49
4.002602
164.93032
1.00794
114.82
126.90447
192.22
55.841
83.80
138.90SS
(262)
2f11.2
6.941
174.967
24.30SO
54.93805
(258)
200.59
95.94
144.24
20. 1797
(237)
58.6934
92.90638
14.00674
(259)
190.2
15.9994
106.42
30.973762
195.08
Atomic
Na.....
Symbol
...........
....
"'-ic
..........
Atomic
No-
Symbol
Atomic
oight
127.60
158.92534
204.3833
232.0J81 ..
Plutonium
Pu
94
(244)
TeDurium
Te
52
Polonium
(209)
Po
84
Terbium
Tb
6.S
Potassium
K
19
39.0983
Thallium
n
81
Praseodymium
Pr
S9
140.90765
Thorium
90 -dl-7 - Th
Promethium
(145)
Pm
61
Thulium ,
69
168.93421
f Tm
Protactinium
Pa
91
231 .03588
Tin (:tannum)
Sn
so
118.710 J
rt..., Ti
Radium
,
.,
47.88
Ra
(226)
88
Titanium
22
Radon
Rn
(222)
"74
86
183.85
<;:from) W
Rhenium
Re
1S
186.207
109
(267)
Unnilennlu
,
, <Une
1
Rhodium
Rh
45
102.90550 I
UnnilheKium
Unh
106
(263)
Rubidium
Rb
37
85.4678
Unniloctium'
Uno
108
(265)
Ruthenium
(262)
Ru
44
101.07
Unnilpentium
Unp
105
Sama.rium
(261)
Sm
62
IS0.36
Unq
104
Scandium
107
, (262)
Sc
21
44 .9S5910
Unnibeptium'
Uns
Selenium
18.96
o#
34
Uranium
u
92
Se
{ 238.0289
n
Silicon
14
28.0855
Vanadium
v
Si
S0.9415
Silver
Ag
47
107.8682
54
131.29
Xe
Xeoon
Sodium
II
22.989768
Yuertium
70
173.04
Na
" Yb
Strontium
Sr
38
87.62
Yttrium
32.066
Sulfur
s
16
Zn
t' 30
6.S.39
Zirconium
Tantalum
180.9479
' 40
91.224
Ta
13
Zr
43
(98)
Technetium
Tc
From the nbk of WQahu 1989 by the Commiuion on Alomk Weiahts, IUPAC (/'u,, Appl. Clltf!l. m1, 61. 97$-1002). Wc:ilhb
are s.:oled to lhe relative aiC>CIW: mass M"'C> 12.
I'
Tilt rwnes in pardllheses ore the l.aJin rorms used in eoonplex l'onnation (ueepl ror wotrrat'll): aold (o...,m); [Aua.r is
..
,,
.. .
...
Zinc .
.
......
..,
llll.
...

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Inorganic Chem.

Sponsoring Editor: Jane Piro

Inorganic Chemistry: Principks of Structurt! and Rcoclivil), Founh Edition

What Is Inorganic Chemistry?

Inorganic Chemistry. the Beginnings

The Structure of the Atom

The Polyelecaronic Atom 20

Symmetry and Group Theory 46

Bonding Models in Inorganic Chemistry: 1. Ionic Compounds 92

Bonding Models in Inorganic Chemistry: 2. The Covalent

The Structure and Reactivity of Molecules 203

The Solid State 252

Chemical Forces 290

Acid-Bose Chemistry 318

Chemistry in Aqueous ond Nonaqueous Solvents 359

Coordination Cllemistry: Bonding, Spectra, and Magnetism 387

Coordination Chemistry: Structure 472

Coordination Chemistry: Reactions. Kinetics, and

Thermodynamic and Kinetic Slability 547

Some Descriptive Chemistry of tfte Metals

General Periodic Trends 578

The Chemi.stry of Elements Potassium-Zinc: Comparison by Electron

Organometallic Chemistry 623

Inorganic Chains, Rings, Cages, and Clusters 738

The Chemistry of the Halogens and the Noble Gases 824

The Use (or Not) of d Orbitals by Nonmetals 866

Reactivity and d Orbital Participation 87S

The Inorganic Chemistry of Biological Systems 889

The Biochemistry of Iron 935

Medicinal Chemistry 954

The Literature of Inorganic Chemistry A-1

Units and Conversion Factors A-3

Atomic States and Tenn Symbols A-7

Character Tables A-13

Bond Energies and Bond Lengths A-21

An Overview of Standard Reduction Potentials of the

Tanabe-Sugano Diagrams A-38

Models, Stereochemistry, and the Use of Stereopsis A-40

The Rules of Inorganic Nomendature A-46

thank colleagJJes in departments that we have visited o n sabbatical leaves: Fred

Excerpts from the Preface

Excerpts " - the Prefoc:e to the Tllinl Editioo.

years, including love, support, and w:uchine their dining

I What h I n tganic Chemlal ry?

reduction of metal o11ides, ca rbonates, and sulfides to the free meulls:'

[Copper/ Bronze Age, ca. 4500-7500 years ago)

[ Iron Age, from ca. 4500- 3500 years ilgO to preSent)

Wanting to choose a single chemicnl system, somehow representutive of inorganic

1 The fiBI chemical

It WllS discovcrcd along the ColumbO Riv<r, WIISI!inJion, by aroup

What Js Jnooanic ChmlaJry?

Whon you buy un

I Who I h horganh Chemlslry?

Scbw<izer. E. K. N01o1u l990, J4f, 524-526.

Whot h Ino rganic Chemistry?

Fig. 1.2 Scanning tunneling

t Whot is lnorgouc Che mistry?

Fig. 1.4 meta-Xylene (left) and ,..,a-xylene (right) an :1 channel in

xylene isomers. The

Ot,OHoFig. l.S llhtStr:uaon or shope sclcctivaty (Csocscry, S. M

8r11 t911S, :!I. 473 - 477.

Whol Is Inorganic Che,..lshy?

C3lled Morganomemllic chemistry,M that