Isolobal Analogy

Roald Hoffmann
Organic Structures

O
R R

O
 Systemization in organic chemistry
!R is any alkyl group CH3 , C2H5, C6H5
!Similarly H can be replaced by any R group.
! =CH2 can be replaced by any CR2 group or
oxygen!

Transition metal Chemistry?

Organometallic Chemistry?
Common fragments
 Organic Fragments
CH4 saturated organic fragment.

Remove hydrogens one by one

CH3.
CH2
CH
 Inorganic Fragments
Start with Cr(CO)6
Relationship between the two?
Remove hydrogens one by one
CH3.
CH2
CH
Evolution of metal Orbitals

n+1 p

n+1 s

nd
 Evolution of metal Orbitals
n+1 p

n+1 s

nd
s + 3p produced 4 hybrid orbitals
sp3
 Evolution of metal Orbitals

n+1 p

n+1 s

nd
 ML6 orbitals

t2g
 ML6 orbitals

t2g
 Basis of 18 electron rule

t2g
 ML5 orbitals

t2g
 Making the fragment

t2g
 Mn(CO)5 d7
.CH
3

Not isostructural fragments

Not isoelectronic either...
A comparison of the frontier
orbital...

They are isolobal!

Results of a computation!
What will a methyl radical do?
What will a methyl radical do?
 Evolution of metal Orbitals

n+1 p

n+1 s

nd
ML4 fragment
 ML4 fragment

t2g
 Mendeleev s Abacus

4 5 6 7 8 9 10
Ti V Cr Mn Fe Co Ni
Zr Nb Mo Tc Ru Rh Pd
Hf Ta W Re Os Ir Pt

a1 b2 #
b2 a1

t2g
 Fe(CO)4

40
Carbene type reactivity

Fe2(CO)8
Unsaturated molecule like olefin but
not stable at RT!
32 However, is stable!
Understanding Complex Structures
 ML3

n+1 p

n+1 s

nd
 Co(CO)3

a1 e
e a1

t2g
 Co(CO)3

a1 e
e a1

t2g
 LUMO (37) (38)
Co(CO)3

HOMO (36)
Structures formed by units
isolobal with C-H
 Simple analogy...

d7 ML5 CH3

d8 ML4 CH2

d9 ML3 CH
What would happen if you
removed two trans ligands?

n+1 p

n+1 s

nd
a1

z2
t2g
 d10 ML2

a1

z2
t2g
BUILDING BRIDGES BETWEEN
INORGANIC AND ORGANIC
CHEMISTRY
ROALD HOFFMANN
Nobel lecture,
8 December 1981
Angewandte Chemie International Edition in English
Volume 21, Issue 10, pages 711724, October 1982
 C-H N

As if the proton has been pushed into the nucleus

of the C !

BH2 C-H N
Non-carbon Bread..
1 FEBRUARY 2002 VOL 295 SCIENCE 832
Selected bond distances ():
P1-P2, 2.1608(11); P1-Ti, 2.5617(8);
Fluxional Organometallic
Molecules
Molecular Gymnastics
 Molecular Gymnastics
Static Crystal Structures

Walk
Talk
Dance..
Mechanisms of Organotransition Metal Reactions

Classification of OM Reactions
M - C

A. Rearrangements, Isomerizations

M - L M - L'

B. Ligand Insertion Reactions

X

M L + X M X L

C. Oxidative Addition Reductive Elimination

Mn+ + L M(n+x)+ L

D. Reactivity changes on the Ligand

M L + Y M L' + X
Rearrangememts Ligand
MLn
MLn Rearrangements
Isomerisation
(CO)3Fe

Fe(CO)5

Cl
RhCl3. 3 H2O
Rh Rh

Cl

Fluxional behaviour

CH3 CH 3
Fe Fe

5 H (s) on unsubstituted ring

 Molecular Breathing
Fe(CO)5
 Berry Pseudorotation
Fe(CO)5
 Molecular Breathing
Fe(CO)5
Carbonyl Hopping
Carbonyl Hopping in Clusters
Metal Hopping
Cis Trans isomerism & CO Hopping
Simple Rotational Isomers
 A molecular propeller!
Rh
. . . .
Rh H All protons equivalent
H H H
at RT

. . . A
.
H H H H H H

Rh
B
H H

Rh . .
Rh
+ H H. H H

.
. . .
H H H H

0 . At RT Spectrum shows only a 2JRh-H av. 2.1Hz

At - 25 Rotaion Stops
Rotation stops,CdCD Solvent
Cl2 Cl
2 2
2 distinct peaks for inner and outer protons A Average 2J
Rh-H

2J
Rh-Hi 1.8 Hz B Expect loss of Rh-H
2J
Rh-Ho 2.5 Hz
Isomerization of Diastereoisomeric
Re-Styrene Complexes

Gladysz, J. Am. Chem. Soc., 1992, 114, 4174.

Reaction Scheme

Gladysz, J. Am. Chem. Soc., 1992, 114, 4174.

Enantiotopic exchange without olefin dissociation
 Possible Intermediates

Slipped' Carbocation Alkylidene Intermediate

2-arene intermediate
 Slipped' Carbocationic Intermediate

Ruled Out

Not Observed
Isomerization can occur by a simple rotation of the =CHR terminus? No

Ph
H
 Alkylidene Intermediate

Ruled Out

Not Found ----- There is no 1,2-H shift taking place

 2-arene complex as an intermediate

Ruled Out

Reactions of phenyl complexes Replacement of benzene by solvent

 Carbon-Hydrogen bond
complex?

k(H)/k(=CHDE) = 1.6 --------- Agostic interaction!!!!!!

Monodendate Bidendate
 Molecules are dynamic
Watch Jason Gatson on parallel bars
Allene Fluxionality
MOs of allene

0.02 eV

-7.5 eV
HOMO
Ring Whizzing
Cyclopentadienyl Haptotropy
Importantly, the Cp is a ligand which can adjust the electron donation
By sliding the metal along the line shown by the arrow
4 C are interacting
CH3 Very rare!
H3C CH3 H M H

H3C CH3 M H
H
H

H
Allyl like coordination

M
 Ring Whizzing
Single line at RT
Cp Cu PEt3
Cu

PEt3

In SO2 at -700 one obtains a typical A2B2X pattern.

S
3
H CuPEt Cu
3

Cu color coded

PEt3
H
3 2 Cu
1,3 Shifts 2
H 3
4 1
4 1
5 Cu
5
2 H
1,2 Shifts 3
Cu
4 3 2
1
3 2
5 4 1
H
4 1 5
H
5 Cu
Cu
1,2 shifts

Atm Cu at 2 Cu at 1 Cu at 5

1 B A B
2 A B C
3 B C C
4 C C B
5 C B A

C and C will change only the time

B,B will change all the time
A will change all the time
Atm Cu at 3 Cu at 1 Cu at 4

1 C A C
2 B B C
3 A C B
4 B C A
5 C B B

B and B will change only the time

C,C will change all the time
A will change all the time
 1,2 Shift 1,3 Shift Random

A Nuclear Magnetic Resonance Study of

v-Cyclopentadienyl ( triethylphosphine ) copper ( I)
George M. Whitesides and John S. Fleming
Journal of the American Chemical Society / 89:12, 1967 p 2855-2859
Fluxional Behaviour of Allyls
 During Reactions
Nucleophilic attacks at a Ru centre
SN2 anti approach
Movie of TS2 in SN2 anti approach of a complex

39
 Fluxional behaviour is associated with
several structures having similar energy

Energy of activation for going from one

minima to the other is small.

18 ve. To 16 ve to 14 v.e is easy..

Steric'and'Electronic'Eects''
of''
Suppor3ng'Ligands'
 In'which'ligands'are'steric'eects'
important?'
CO'
NO+'',''CN@,'''

PR3'
Carbene'complexes'and'NHC''
Isocyanides'R@NC'

@
H '
 Concepts'
Steric'inuence'exerted'by'the'ligand.''
A'radius?'Or'just'an'angle?'Is'it'a'volume?'
These'are'nebulous'parameters'in'chemistry.'
'
Tolmans'cone'angle'
Nolans'Buried'Volume'
'
van'der'Waals'radius,'covalent'radius,'ionic'
radius''
Non@spherical'distribu3ons'of'the'electron''
cloud!'
Tolmans'Cone'Angle'
 Phosphines:*Key*Features'
A'versalite''acceptor'PR3'''
Electronic'proper3es'of'PR3'can'be'tuned'by'varying'R.'
Although'not'as'good'as'CO,'it'has'a'variable'steric'inuence.'

The*STERIC*inuence*of*R*groups*in*PR3*gives*us*an*advantage*
Problem:''The'angle'at'M'depends'on'the'M@L'distance!'

SOLUTION:'''''FIX'it'at'an'average'distance'2.28'''
 Quan3fying'Steric'Eects'
Cone*angle*measured*by*Tolman*is*the*simplest*/*
fastest*measure**of*the*steric*requirement.*
Using*space*lling*models,*he*constructed*physical*
models*and*measured*the*angle*using*a*protractor.***
**************
PH3* ************I * *87*
PF3 * ************I * *104*
PMe3 * *I * *118*
PPh3 * *I * *145*
P(tBu)3 * *I * *182'
 Does'it'ma^er?'
COMPLEX* * Kd*

P(OEt)3* 109* 10I10*

P(OiPr)3* 114* 2.7x10I5*
P(OIpTol)3* 121* 6x10I10*
PMe3* 118* 10I9*
P(Et)3* 132* 1.2x10I2*
 Importance'of'Steric'Eects'
Pd L4 Pd L3 Pd L2

Me3P PEt3 PCy 3 PPhBu2

As'you'put'more'and'more'bulky'groups,'the''complexes'on'the'
le`'side'become''less'and'less'stable.''The'equilibrium'shi`s'to'
the'right.'
 Steric'forces'of'the'ligand'changes'the'
structure!!'
Extreme'example'is'[CoL4]+''
Here'L'is'P(OiPr)3''''
'
d8'complexes'prefer'square'planar'structures'
and'not'octahedral'or'tetrahedral.'''''''''''Why'?''
Dierence'in'energy'required'for'Oh'd2sp3'and'SqP'
dsp2'suggests'that'the'la^er'is'be^er'when'M@L'
bonds'are'weak!'(not'strong'enough'to'
compensate'for'mixing'in'pz)'
'
A'choice'between'Td'and'SqP'complexes'depends'
on'LFSE'dierences''('bonding'is'poorer'in'Td,'no.'
of'd'electrons)'''and'steric''pressure'favor'Td!'
''
The'Co'complex'is'tetrahedral'showing'
importance'of'steric'eects'!'
 Tolmans'angle'is'not'just'steric!'
It'is'stereoelectronic! ''
R' '''''cone'angle'in' ' Two'ways'in'which'it'is'electronic!'
' ' 'PR3' '
1.'Smaller'ligands'can'come'closer'while'
' ' '' larger'ligands'bump'into'one'another'and'
H''''''' ' ''''87' stay'far'from'the'metal!'Poor'bonding'
'
OMe'' ' '107' 2.'If'the'ligand'is'more''bonding,'it'will'
Me'''''' ' '118' come'closer'to'the'metal'and'cone'angle'
would'increase!''
Et''''''''' ' '132' '
Unfortunately'it'was'ini3ally'done'with'
Ph'''''''' ' '145' models'
F'''''''''' ' '104' '

tBu''''''''' '182'
Mesityl''' '212''
 Tolmans'cone'angle'from'crystallographic'data.'
'
Determina3on'of'Tolmans'cone'angle'from'crystallographic..'Data'Base'
Muller'T.'E.'and'Mingos'D.M.P.'
Transi3on'Met.'Chem.'20,'533,'(1995).'*'
 Complica3ons'with'P(OR)3''
Steric'parameters'of'.Environments''
Smith'J.M.'and'Coville'N.J.''
Organometallics''2001,'20,'1210@1215.'

R'='Me'
 A'tale'of'two'ligands'
'Special'Ligand'no.'1:'N@heterocyclic'carbenes'
'Special'Ligand'no.'2:'The'hydride'
 NHC'are'super'heroes'
A'comparison'between'nickel'and'palladium'precatalysts'of'1,2,4@
triazole'based'N@heterocyclic'carbenes'in'hydroamina3on'of'
ac3vated'olens'
Chandrakanta'Dash,'Mobin'M.'Shaikh,'Ray'J.'Butcher'and'
Prasenjit*Ghosh*
Dalton'Trans.,'2010,'39,'2515@2524'
Beyond catalysis: N-heterocyclic carbene
complexes as components for medicinal,
luminescent, and functional materials
applications
Laszlo Mercs and Martin Albrecht

Chem. Soc. Rev., 2010, 39, 1903-1912

N-Heterocyclic Carbenes in Late Transition Metal

Catalysis

Silvia Dez-Gonzlez, Nicolas Marion and Steven P. Nolan

Chemical Reviews 2009109(8), 3612-3676
 Steric'proper3es'of'NHC'
A'neutral'ligand'with''acceptor'capability'
Very'good'sigma'dona3on'
Tunable'electronic'and'steric*property*
Ligand'is'easily'synthesized'in#situ#
NHC*are*super*heroes!*
Steric'Features'

Will'rota3on'around'the'M=C'bond'change'the'cone'angle?'
Nolans'buried'volume'

M@C'bond'length'2.0'Angstroms'

3.5'angstroms'
 Steric'Features'
'
Percent'buried'volume'for'phosphine'and'N@heterocyclic'carbene'ligands:'
steric'proper3es'in'organometallic'chemistry''
Clavier,'Herve;'Nolan,'Steven'P.'
Chem.'Commun.'2010,'46,'841@861'''DOI:'10.1039/b922984a'''''

A'por3on'of'this'volume'in''this'
imaginary'sphere'of'3.5''radius''
is'occupied'by'each'ligand.'
'
%'used'by'the'ligand'is'called'the'
buried'volume.'
 WIRE'FRAME'MODEL'
ADUVOL'from'the'CSD'
trans@bis(1,3@bis(2,4,6@Trimethylphenyl)imidazolidin@2@ylidene)@dichloro@nickel(ii)'
 SPACE'FILLING'MODEL'
ADUVOL'

trans@bis(1,3@bis(2,4,6@Trimethylphenyl)imidazolidin@2@ylidene)@dichloro@nickel(ii)'
Metal'ion'dependence'

No.* R* %*buried* %*buried*

volume** volume**
(M=Cu)* (M=Ag)*
*
1' cyclohexyl' 29' 28'
2' Mesityl' 36' 36'
3' Adamantyl' 37'
4' tButyl' 37'
5' Di'@sopropyl'phenyl' 48' 46'
 BDE'''in'Kcal'/'mol'
'
I@Mesityl'' '41'
''
SI@Mes'''''''' '40''''(S'stands'for'saturated'I'ring)'
'
I@Adam' ''''' '20'
'
I@tButyl'''''' '24'

No.* R* %*buried*
volume**
(M=Cu)*
1' cyclohexyl' 29'
2' Mesityl' 36'
3' Adamantyl' 37'
4' tButyl' 37'
5' Di'@isopropyl'phenyl' 48'
 Steric'Eects''
Approxima3ons'are'required'to'quan3fy'steric'eects!''
'(a)'Angle'subtended'at'the'metal'using'a'xed'M@L'distance.'
'(b)'The'%'volume'occupied'by'the'solid'cone'in'an'imaginary'
sphere'around'the'metal'and'a'xed'M@L'distance.''
'
Ignore'M@L'bond'distance'eects.'

Use'crystallography'to'make'it'more'realis3c:'corrects'for'the'
errors'men3oned'above!'
 Caveats'in'using'steric'eects'
Size'of'the'balloon'depends'on'how'much'you'squeeze'the'balloon'with'the'
Vernier'calipers'you'are'using'to'measure'the'baloon'with!'P(OR3)3''
'
Es3ma3ng'the'solid'angle'or'the'cone'angle'can'be'computed'using'a'
computa3onal'model':'
*SambVca:'A'Web'Applica5on'for'the'Calcula5on'of'the'Buried'Volume'of'
*NIHeterocyclic*Carbene*Ligands*
*Poater*A.,Cosenza*B.,*Correa*A.*,*Giudice*S.,**Ragone*F.,*Scarano*V.*and*Cavallo*L.'
#Eur.#J.#Inorg.#Chem.#2009,'17591766'
'URL'h^p://www.molnac.unisa.it/OMtools.php.'

Improved*Algorithm*for*Accurate*Computaeon*of*Molecular*Solid*Angles*
B.*Craig*Taverner'h^p://www.gh.wits.ac.za/craig/steric/mul3sol/html/mul3sol.html'
 A'brief'comment'on'the'Hydride..'
Smallest'ligand'known'in'chemistry.'
What'is'its'size?'
 Hydride..'

Hydrogen'occupies'a'coordina3on'
site'on'the'metal.''
Structures'of'metal'hydrides!'
Flexible'steric'eects!'

HRh(CO)(PPh3)3 HRh(PPh3)4
 RhHCO(PPh3)3*

P@Rh@P'angle'is'120o'
 RhH(PPh3)4*

P@Rh@P'angle'is'~'109o'
RhH(PPh3)4*
 Electronic'Eects'
Quan3ca3on'of'electron'dona3on:'
Tolmans'Electronic'Parameter'TEP'
(See'the'video'lecture'on'subs3tutes'for'CO'and'the'
lecture'on'N@heterocyclic'carbenes)'
'''
 Quan3fying'Electronic'Eects'
Be^er'to'look'at'a'series'of'complexes.'

Tolman'did'this'with'[Ni(CO)3(L)]'where'the'L'is'a'NHC.'
He'quan3ed'the'symmetric'stretch'of'the'3'CO'
ligands'as'a'func3on'of'L'

L'='CO'''TEP'is'2060'

The'average'CO'stretch'is'called'the''
'''''Tolman'electronic'parameter.'(TEP)'''
'
 Electronic'Character'of'NHC'
13C'chemical'shi`'in'a'Pd(II)'complex'is'used'

as'a'probe.'Chemical'shi`'increases'with'
NCN'angle'
Usually'on'complexa3on,'the'
chemical'shi`'goes'upeld'
by'30'ppm.'180'ppm.'
 Quan3ta3ve'Analysis'of'the'Ligands'
Electronic'Eects'
ECW''Model'of'R.S.'Drago'
Property'='EaEb'+'CaCb''+W'
Does'not'model'the'steric'eects'of'ligands'

'
''
Quan3ta3ve'Analysis'of'Ligand'Eects'
QALE'method''Developed'by'Giering'and'Prock'
Property'=''a''+'b'+'c'(@'st')'+'dEar'+'e'''
''''//a,'b,'c,'d,'e'is'determined'for'each'property//'
'is'the'electronic'parameter'and''the'cone'angle'(Ar'is'no.'aroma3c'
rings)'
*
Comments*on*Coupling*Graphical*and*Regression*Analyses*of*Ligand*
Eect*Data*
Bartholomew'J.,'Fernandez'A.'L.,'Lorsbach'B.A.,'
Wilson'M.R.,'Prock'A.,'and'Giering'W.'P.'
Organometallics#1996,'15,'295F301'
 An'Example'of'QALE'

0'

@2'
Kine3cs'of'the'dissocia3on'' log'k'
Plo^ed'against'cone'angle'
@4'
'
The'break'at'160'indicates'a'threshold'
for'the'steric'parameter!' @6'
100''''''120''''140''''160''''180''''''200'
Cone'angle'in'degrees.>'
 QALE'and'thermodynamics'

@H'#=##70.73()###0.10'#@'0.461(#7#135)##0.026'@'1.68Ear##0.34'+'46.3'#0.8'
'
r2#=#0.964######n#=16'
Nega3ve'coecient'indicates'that'heat'of'reac3on'increase'as'the'phosphines'
become'be^er'donors'
For'this'reac3on,'there'is'no'steric'eect'3ll'the'Tolman'angle'reaches'135.'
Data'from'PR3'and'PAr3''fall'on'two'dierent'lines'when''is'plo^ed'against'H.''
If'there'is'no'aroma3c'ring'eect'the'lines'cross'at'#=#4.8#'
'
 QALE'
Proper3es'can'be:'Thermodynamic'data'(pK values,#E a#

#values,#heats#of#reacIon,#equilibrium#constants),'
bond'lengths,'and'NMR,'IR,'UV/vis,'photoelectron,'
and'Mossbauer'spectroscopic'data'

Recent'example:'Quan3ta3on'of'the'ligand'eect'in'oxo@transfer'
Reac3ons'of'dioxo@Mo(VI)'trispyrazolyl'borate'Complexes''
'' 'Partha'Basu,'Brian'W.'Kail,'Andrew'K.'Adamsa'and'Victor'N.'Nemykinb'
Dalton'Trans.,'2013,'42,'30713081'
 Quan3fying'S&E'Eects!'
It'is'possible'to'quan3fy'steric'eects'from'
crystallographic'data!'Use'with'cau3on!'
Electronic'eects'from'spectroscopic'data!'

To'have'predic3ve'value,'one'needs'to'include'
both'steric'and'electronic'eects!'