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M C O M C O
bond
A B bond Organometallic
Chemistry
6.1. INTRODUCTION
Organometallic chemistry is the branch of chemistry that acts as a bridge between organic
chemistry and inorganic chemistry. Its importance lies in the production of new reagents and catalysts
which are used in the preparation of useful compounds. For example, with the use of Grignard
reagents, which are organometallic compounds of magnesium and alkyl lithiums, we can prepare
almost any class of organic compounds. Structural determination of ferrocene, an organo metallic
compound of iron has added to our knowledge regarding the formation of chemical bond. These are
the compounds that contain a direct linkage between a metal atom and one or more carbon atoms.
It is a rapidly growing and promising field of chemistry and we can expect to produce substances
having versatile properties using organometallic compounds.
CH2
Pb (CH2CH3)4 Cl
Tetraethyl lead CH2
+
Fe K Pt
Zn (CH2CH3)2 Cl Cl
Diethyl zinc
Ferrocene Ziese salt
Compounds like aluminium triethyl, sodium acetate, etc. do not qualify to be organometallic
compounds because, the metal is not directly linked to carbon, but to oxygen in the above stated
compounds.
OC2H5 O
Al H3C — C — O Na
Sodium acetate
C2H5O OC2H5
Aluminium triethoxide
148
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ORGANOMETALLIC CHEMISTRY 149
Also metal cyanides (M—CN) and metal carbides like CaC2 and Al4C3 are not included in
organometallic compounds because they show properties of compounds studied in inorganic
chemistry, although these metal cyanides and carbides contain a metal-carbon bond.
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150 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
2. Two carbon bonded ligands. These are the molecules in which two carbon atoms of the
ligands are bonded to the metal atom. These are called dihapto ( 2) ligands (or two-electron
donors).
M or M
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ORGANOMETALLIC CHEMISTRY 151
Examples of such ligands are alkenes or alkynes in which both the carbon atoms at each end
of the multiple bond are involved in forming the metal-carbon bonds. The bonding in these ligands
is indicated either by two dotted lines to the participating carbon atom or a single solid line from
the centre of the participating carbon atoms of the ligand to the metal atom.
3. Three carbon bonded ligands. These are the molecules in which three carbon atoms of
the ligands are bonded to the metal atom. These are called trihapto ligands (). Examples
of such ligands are allyl group (C3H5) known as -allyl ligands as shown below. These may be
distinguished from -ally1 complexes in which the allyl group is bonded through one carbon atom only
(monohapto).
H M
H
H CH2
H C H C
H C
C C or C H CH
H M
H H
M H2C
- Allyl complex - Allyl complex
4. Four carbon bonded ligands. These ligands contain four carbon atoms which may be
bonded to the metal atom. Therefore, these are called tetrahapto (4-electron donors) or
ligands. These include acyclic ligands such as 1,3-butadiene and cyclic ligands such as
cyclobutadiene.
HC CH HC CH
or or
M H2C CH2
H2C CH2
M M
5. Five carbon bonded ligands. These ligands comprise molecules in which five carbon atoms
of the ligands are bonded to the metal atom. These are called pentahapto ( ) ligands. The
common examples are acyclic dienyls and cyclic dienyls (e.g., cyclopentadienyl).
H
HC
C
HC CH
or HC CH or
H2C CH2 HC CH
M
M M M
Pentadienyl Cyclopentadienyl
6. Six carbon bonded ligands. The molecules in which six carbon atoms of the ligand are
bonded to the metal atom. The common example of such a ligand is benzene. The common example
of an organo-metallic compound is dibenzene chromium (C6 H6 )2 Cr. This is also a sandwich
compound in which Cr atom is present in between two benzene rings.
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152 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
Cr
7. Seven carbon bonded ligands. These ligand comprise molecules in which seven carbon
atoms act as electron donors by participating all the seven carbon atoms in bond formation. A common
example is cycloheptadienyl (– C7 H7) as shown below:
C
C C
C C
C C
M
Cycloheptadienyl
8. Eight carbon bonded ligands. These ligands comprise molecules in which eight carbon atoms
are involved in bond formation. These are also called octahapto ligands. A common example of
such a ligand is cyclo-octatetraene (C8H8). A common example of the complex is U (C8H8)2.
Fe(CO)3 Mo(CO)3
Cyclooctatetraene Cyclooctatetraene
4–electron donor (6–electron donor)
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ORGANOMETALLIC CHEMISTRY 153
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ORGANOMETALLIC CHEMISTRY 155
Electrons in V (–1) = 24
Six CO groups give two electrons each (6 ×2) = 12
EAN = 36
–
Thus, V (CO)6 obeys EAN rule.
(ii) They may form single covalent bond with an atom or group having a single unpaired electron,
e.g., hydrogen (H) or chlorine (Cl) [ H M(CO)n] or [ M (CO)n Cl ]. For example,
Mn (CO)5 Cl
Electrons in Mn(0) = 25
5 CO groups give two electrons each (5× 2) = 10
Cl = 1
EAN = 36
EAN for Mn (CO)5 Cl = 36
Similarly, H Co (CO)4
Electrons in Co(0) = 27
4 CO groups give two electrons each (4 × 2) =8
H =1
EAN = 36
(iii) If no other species is available with which the metal carbonyl containing odd number of
electrons can interact, it can dimerize resulting in pairing of electrons. This will lead to the formation of
metal-metal bond. While counting the EAN, the electron pair shared between two metal atoms form-
ing metal-metal bond is counted on both the metals.
For example, manganese forms a stable dinuclear carbonyl, Mn 2 (CO)10 having metal-
metal bond, (CO)5 Mn – Mn (CO)5. Let us calculate EAN for this complex.
Mn2 (CO)10
Electrons in 2 Mn (2 × 25) = 50
10 CO groups give two electrons each (10 × 2) = 20
One Mn–Mn bond =2
EAN for Mn2 (CO)10 = 72
EAN per Mn atom = 36 (Kr)
EAN rule for other Organometallic Compounds
EAN rule can also be applied to other organometallic compounds. For this purpose, number of
electrons donated by various ligands are taken into consideration.
Let us illustrate the calculation of EAN for some complexes.
(a) Alkyl groups as 1 electron donors
CH3 Re(CO)5
Electrons in Re (Rhenium) = 75
5(CO) give two electrons each (5 × 2) = 10
CH3 =1
EAN = 86
(b) Olefins and alkynes acting as 2-electron donors
[ Mn(CO)5 C2 H4 ]+
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156 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
Electrons in Mn+ = 24
5 (CO) give two electrons each = 10
Contribution from C2H4 =2
EAN = 36
(c) -allyls acting as 3-electron donors
Mn(– C3 H5 ) (CO)4 Co (– C3 H5)(CO)3
Electrons in Mn = 25 Electrons in Co = 27
Contribution of – C3H5 = 3 Contribution of – C3H5 = 3
4 (CO) contribute = 8 3(CO) donate = 6
EAN = 36 EAN = 36
(d) π -cyclo pentadienes as 5-electron donors
Co (– C5 H5 ) (CO)2 Fe (C5 H5 )2
Electrons in Co = 27 Electrons in Fe = 26
Contribution of 2 ( π – C5 H5) = 5 Contribution of 2 (– C5 H5) = 10
2 (CO) donate = 4 EAN = 36
EAN = 36
Thus, it has been observed that most of the organometallic compounds obey EAN. There are
some exceptions also in which EAN rule is not obeyed. For example,
Co (– C5 H5)2 Cr (C6 H6 ) (CO)4
Electrons in Co = 27 Electrons in Cr = 24
Contribution of 2 ( – C5H5) = 10 Contribution of C5H5 = 6
EAN = 37 Contribution of 4 (CO) = 8
EAN = 38
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ORGANOMETALLIC CHEMISTRY 157
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158 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
Reactive
Intermediates
The formation of alkyl radical leads to subsequent reactions.
(iii) Hydrogen transfer from alkyl to metal. The higher alkyl organometallic compounds
particularly those which carry -hydrogen are unstable. -hydride elimination reaction provides an
opportunity for the decomposition of metal alkyls into a metal hydride and olefin. (-elimination
reaction may be represented as
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ORGANOMETALLIC CHEMISTRY 159
H H
M—C—C—R M – H + CH2 = CHR
H H
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160 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
Li
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ORGANOMETALLIC CHEMISTRY 161
LiR + R I
LiI + RR
(b) Reactions with proton donor give the corresponding hydrocarbons. For example,
LiR + H+ Li+ + RH
(c) Reactions with metal carbonyls give aldehydes and ketones. For example,
–
O
||
Li+ R – C – Ni (CO)3
LiR + [Ni (CO)4]
The intermediate unstable acyl nickel carbonyl complex can be attacked by electrophiles such
as H+ or R Br to give aldehydes or ketones by solvent induced reductive elimination.
O
—
—
So
Li+ [R — C — Ni (CO)3] –
R
B r O
So
—
—
lv
en
Ketone
(d) Reaction with halogens gives parent alkyl (or aryl) halide. For example,
LiR + X2
LiX + RX
(e) Reaction with CO gives symmetrical ketones. For example.
2LiR + 3CO
2LiCO + R2 CO
(f ) Reaction with ethers gives alkenes; the organometallic reacts here as a very strong base
(proton acceptor). For example,
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162 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
(g) Metal-halogen exchange reactions give other organometallic compounds. For example,
3LiR + BC13
3LiC1 + BR3
4LiR + SnC14
4LiC1 + SnR4
3LiR + P (OEt)3
3LiOEt + PAr3
(h) Reaction of lithium aryls (behaving as typical carbanion) in non-polar solvents with CO2
gives carboxylic acid and with aryl ketones gives tertiary carbinols. For example,
H 2O
LiAr + CO2
ArCO2 Li LiOH + ArCO2H
LiAr + Ar2 LO H 2O
[Ar2 C (Ar) OLi] LiOH + Ar
Ar 2 C (Ar) OH
(i) Reactions with N, N- disubstituted amides give aldehydes and ketones. For example,
LiR + R CONMe2
LiNMe2 + R COR
Structure. Lithium alkyls are H
polymeric and generally exist as H
tetrameric units such as (Li CH3)4. In Li C
lithium methyl there is a tetrahedral set of H
four lithium atoms with a methyl group
placed symmetrically above each Li 3 H
face. The structure clearly involves a H C Li
methyl group bridging three lithium H
atoms. The C-atoms have coordination H
no. 7 being bonded directly to three H H
and four Li atoms. The Li – C distance is C H Li
231 pm. The Li-Li distance in the
structure is 268 pm which is identical
with the value of 267.3 pm for a gaseous
Li2 molecule and smaller than the value Li C
of 304 pm in Li metal. H
Structure of (LiMe)4 H H
Applications of organolithium compounds
The important applications of organolithium compounds are given below:
1. Organolithium compounds are used as catalysts in polymerisation reactions. For example,
n-BuLi catalyses polymerization of butadienes. If butadiene is polymerized in the presence of
catalysts such as Co or Ni some metal impurities are always left in the reaction mixture but with
organolithium compounds there is no such problem. These factors provide advantages in certain
applications such as impact resistance modifications of plastics.
2. Organolithium compounds are also used as precursors to metalated organic reagents.
3. The organolithium compounds are useful synthetic reagents and have been increasingly
used in industry and laboratory. Alkyl and aryl lithium derivatives are extensively used in place of
Grignard reagents because of the advantage of easier handling and higher speed of the reactions.
For example, PhLi is about 100 times more reactive than Mg Br.
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ORGANOMETALLIC CHEMISTRY 163
4. The allyllithium compounds combine with butadiene and tend to copolymerize with
monomers such styrene to give block copolymers by forming the stable living polymers.
363 K
2A1 + 3Hg Me2 Al2 Me6 + 3Hg
Al2 Ph6 can be prepared similarly using HgPh2 in boiling toluene or by the reaction of LiPh on Al2
Cl6.
Properties. 1. Aluminium trialkyls and triaryls are highly reactive volatile liquids or low
melting solids, which burn in air and react violently with water.
2. They react with protonic reagents to liberate alkanes.
Al2 R6 + 6HX
6RH + 2Al X3
3. Organoaluminium compounds give alkene insertion reactions known as growth reactions
to synthesize unbranched long chain primary alcohols and alkenes. Here alkenes insert into the Al
– C bond of monomeric AlR3 (acting as catalyst) at ~425 K and 100 atom to give long chain
derivatives whose composition can be closely controlled by the temperature, pressure and contact
time.
Long chains of length of 14–20 C atoms can be synthesised industrially in this way and then
converted to unbranched aliphatic alcohols after oxidizing with air and then hydrolysing with water
for use in the synthesis of biodegradable detergents.
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164 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
2 (i) O
Al (CH2 CH2 R )3
(ii) H O+ 3RCH2 CH2 OH
3
4. Al2 R6 (or AlR3) react readily with ligands to form adducts and behave as Lewis acids. For
example,
AlR3 + L (ligand) Li Al R3 (adduct)
(L = amines, phosphines, ethers and thioethers)
5. Aluminium alkyls also combine with lithium alkyls to give mixed alkyls.
In benzene
(C2 H5)3 Al + LiC2 H5 Li Al (C2H5)4
6. They react with halides or alkoxides of elements like B, Ca, Si, Sn etc which are less
electropositive than Al to form other organometallics.
n
MXn
MRn + AlX3
3
7. Organoaluminium compounds bring about low pressure polymerization of ethene and propene
in presence of organometallic mixed catalyst. A Ziegler-Natta catalyst is a mixture of TiC14 and Al2
Et6 in heptane giving a brown suspension which rapidly absorbs and polymerises ethene even at
room temperature and atmospheric pressure. Polyethene produced in this way has superior qualities.
H3C C6H5
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ORGANOMETALLIC CHEMISTRY 165
CH3
2e – 3c bond
H3C CH3
Al Al
H3C CH3
2e – 3c bond
CH3
Bonding in Al (CH3)3
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166 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
CH3
R3Al
2C3H6 CH2 = C — CH2CH2CH3
Propene
R3Al
2C4H8 CH2 = C — CH2CH2CH3
Butene
Et
Hexene (2-methyl pent-1-ene) which is dimer of propylene gives heptanol which is the
important raw material of plasticizers in the oxo process.
5. In the production of linear higher -olefins
Trialkyllaluminium is added in steps to ethylene to form polymeric trialkyaluminium. This
polymeric trialkylaluminium gets substituted by ethylene on heating or in the presence of nickel salt
to produce high linear -olefins as:
120°C Heat
AlEt3 + 3n C2H4 Al [(C2H4)n Et]3 3C2H5 (C2H4)n–1 CH = CH2 + AlEt3
100 atm 3C2H 4
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ORGANOMETALLIC CHEMISTRY 167
Properties
Tetraalkyl and tetraaryl compounds of tin Rn Sn X4–n (n = 1 to 4) are colourless, monomeric
liquids or solids. They resist hydrolysis and oxidation under normal conditions. However, when
ignited, they burn to give SnO2, CO2 and water.
Major reactions of organotin compounds are given below:
1. Triorganotin radical reactions. The R3Sn – H, R3Sn – CH3 and R3Sn – SnR3 bonds are
weak having bond strengths 70 and 65 and 63 k cal mol–1. In the presence of light, these compounds
form radicals easily.
h
R3Sn — SnR3 R3Sn + R3Sn
Radicals
t–BuO + R3–SnSnR3 BuOSnR3 + R3Sn
These radicals react with halides to form new radical as
R3Sn + RX R3SnX + R
Tetraalkyl and tetraaryl compounds of tin i.e. RnSnX4–n are colourless, monomexic liquids
or solids. They resist hydrolysis and oxidation under normal conditions. However when ignited they
burn to give SnO2, CO2 and H2O.
2. Reactions of organostannylenes. Divalent organotin compounds, R2Sn (called
organostannylenes) containing alkyl or aryl are labile. However, other compounds containing
different groups are stable. These provide synthetic routes to obtain higher polystannes as:
2 Et O
SnCl2 + 2[LiCH (SiMe3)2]
0 C
[Sn{CH (SiMe3)2}2]
The compound was obtained as red crystals (m.p. 136°). It is monomeric in benzene.
3. Hydrostannation. The unsaturated compounds such as olefins and acetylenes react with
tin hydride. The reaction is known as hydrostannation reaction. The compound formed has
functional group substituted by organotins in the reaction and tin atom is exclusively attached to
the terminal carbon.
CH2 = CRCOOMe + Me3SnH Me3SnCH2CHRCOOMe
4. Hydrostannolysis. The bond between alkyl (or aryl) group and halogen or sulphur is
cleaved by an organotin hydride. This is called hydrostannolysis reaction and is used for
dehalogenation reaction of a halide.
Br H
Bu3SnH
Cl Cl
Organostannylenes are reactive compounds and undergo insertion and cyclization reactions
as:
Me3Sn Sn Me3 + R2Sn R2Sn (SnMe3)2 (insertion)
O
CR2
R2Sn + R2 CO R2 Sn (cyclization)
O — CR2
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168 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
through tin-halogen bond. The bond parameters in associated Me2SnCl2 are given below.
Me
Me Me
109° Cl Cl 354 pm 109°
124°
Sn Sn Sn Cl
93° pm
Cl Cl Cl 2 40 Me
Me Me
Bond parameters in Me2SnCl2
We observe extensive polymerisation in R3SnX. The associated structure of Me3 SnF is given
below.
Me Me
Me
F F
Sn Me Sn
Sn
F
F Me
Me
Me Me Me
Applications
1. The organotin compounds have bacteriocidal, fungicidal, acaricidal and insecticidal
properties and have strong affinity of tin atoms to a donor ligand atoms such as S, O and N. It is
an important indispensable element in human body.
Organotin compounds which are used in agriculture as fungicides, antifeedants and
acaricides are listed separately as under.
Fungicides : Ph3SnX (X = OH, OAc)
Antifeedants : Ph3SnX (X = OH, OAc)
Acaricides : (C6H11)3 Sn X(X = OH)
2. mono organotin chloride and diorganotin chloride such as monobutyltin chloride and
dimethyltin chloride are used as precursors in forming surface films on SnO2 at high temperatures.
3. Organotin compounds find use as effective wood preservatives. The fungicidal activity of
organotin compounds follows the order.
R3SnX > R4 Sn R2SnX2 > RSnC3
4. Organotin compounds are used as homogeneous catalysts for polymerization of urethenes,
polymerization of silicones and esterifications because of strong affinity to oxygen of organo
compounds. Organotin compounds are also used as polymerisation catalysts for olefins.
5. Organotin compounds are used in textile and glass industry and as water repellant etc.
Bis (tributyl tin) oxide is used for preventing fungal attack on cotton textile and in cellulose based
house hold fillers. Bis (tributyltin) oxide and triphenyltin chloride have biocidal effect against cloth
moth.
6. The organotin compounds have also been used successfully as anthelmintics, disinfectants
and antitumour drugs because they have poisonous characteristics in cells. R2Sn compounds have
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ORGANOMETALLIC CHEMISTRY 169
also been used as anticancer drugs because they block the growth of tumour cells and are also used
for curing hyperbilirubinemia.
Tributyltin compounds are used against gram positive bacteria.
7. Organotin compounds are used as heat and light stabilizers for polyvinyl chloride (PVC)
plastics. The common examples to this effect are (R2SnOCOCH = CHCOO)n (R = Bu, Oct) and
Bu2Sn(OCOCH = CHCOO Oct)2, Bu2Sn (OCOC11 H23)2 etc.
CH3 CH3
room temp.
TiCl4 + 4LiCH2 — C — CH3 CH3 — C — CH2 — Ti
ether
CH3 CH3
4
2. Cyclopentadienyl compounds such as [Ti(5 – C5H5)2X2)] X = Cl, Br, I are more stable.
Dicyclopentadienyl titanium halides may be prepared as:
TiCl4 + 2(C5H5)M (5 – C5H5)2 TiX2
M = MgCl, Mg Br, Na or Li; X = Cl, Br
The same compound has also been prepared by the reaction of cyclopentadiene with TiCl4 in
the presence of diethylamine.
60 – 80° C
TiCl4 + 4C5H6 NHEt2, dioxane
(C5H5)2 TiCl2
3. Organotitanium compounds can be prepared by the reaction of titanium halides with
organometallic compounds such as organoalkali metal compounds. For example, tetrachloro titanium
is mixed with methyl magnesium chloride at –78°C when a dark green solid is precipitated. The
supernatant solution is removed and a solution of ether or hexane as solvent is added to the residue
and concentrated at – 48°C when yellow crystals of tetramethyltitanium are formed.
TiXm + RM RnTiX4–n
M = Li, Na, MgX; X = Cl, Br, R = alkyl
78C
Ti + 4 Me MgCl Me Ti
in ether 4
4. When TiCl4 is added to Al(C2H5)3 in Leptone, a brown solid known as Ziegler Natta catalyst
is obtained. This is a wonderful catalyst and is used for polymerisation of ethylene to straight chain
polyethene.
5. Tetraphenyl titanium is obtained by mixing phenyl-lithium and titanium tetrachloride at –70°:
70C
TiCl4 + 4PhLi
ether
Ph4Ti
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170 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
PROPERTIES
Organotitanium compounds undergo following types of reactions:
1. Substitution reactions. Cyclopentadienyltitanium dichloride gives substitution reactions as:
(C5H5)2 TiCl2 + 2LiNMe2 (C5H5)2 Ti (NMe2)2
2. Tetravalent titanium compounds get reduced to trivalent titanium compounds with metals
such as sodium, magnesium or zinc. The reaction with zinc takes place as under.
1 1
(C5H5)2 TiCl2 + Zn (C5H5)2 TiCl + ZnCl2
2 2
Trivalent titanium compounds, (C5H5)3 TiCl and other lower valence organotitanium
compounds are easily oxidised and therefore, they have strong reducing power. Therefore, they are
used as organosynthetic reagents.
Some common examples of trivalent, divalent and zero valent organotin compounds are
Ti (III) : (C5H5)2 TiCl, (C5H5) TiCl2
Ti (II) : (C5H5) (C6H5) Ti (OEt2)2
Ti (O) : (6 – C6H6)2 Ti
3. Carbo metalation. This reaction deals with olefin polymerisation with titanium compounds.
Titanium reacts with organoaluminium compounds when titanium atom forms a bridged structure (Ti
— R — Al) with an alkyl group of organoaluminium compounds and then Ti—R adds to a carbon-
carbon double bond as shown below.
C C + R – Ti R — C — C — Ti
4. Insertion reactions. Carbon monoxide reacts with organotin compound when the former can
be readily inserted into Ti—R bond as
X(C5H5)2 TiR + CO (C5H5)2 TiCOR(X)
R = Me, Et, Ch2Ph, X = Cl, I
H
Ti
H
Here, two cyclopentadienyl rings act as monohapto (1) and other two rings acts as pentahapto
(5). The structures of carbonyl compound [Ti(5 – C5H5)2 (CO)2] and dimeric Ti(C5H5)2 have
the following structures.
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ORGANOMETALLIC CHEMISTRY 171
C—O H
Ti Ti
Ti H
C—O
Applications
1. Thin film forming materials. The organometallic titanium compounds are used as high
purity single metallic materials for forming thin films. This has advantage over the usual techniques
of vacuum vaporization, wet electroplating and electrodes plating which are difficult to form a
homogeneous pinholeless metal thin film. Organotitanium compounds are used as raw materials for
metal carbides. Titanium carbide formed is useful as abrasion resistant coating material such as lining
of fusion reaction vessels, cutting tools and bearings. etc. TiC coating is carried out by heating TiCl4,
H2 and CH4 and this process is called CVD process (Chemical Vapour Deposition process). The
thin forming process is believed to occur as:
Ti (OCH2CH3)4 + 4LiCH2C(CH3)3 Ti[CH2C(CH3)3]4
CH2
–2C (CH3)4 –2CH2 = C(CH 3)2
Ti[CH2C(CH3)3]4 Ti C(CH3)2
CH2
2
—CH2—Ti—CH2— TiC
In this reaction, elimination of a neopentyl group is accompanied by the elimination of
hydrogen at the -position to form titanium cyclobutane. The elimination of isobutylene gives —
CH2—Ti—CH2—) which finally decomposes to TiC.
2. Anticancer drugs. Organotitanium compounds have also been found to act as anticancer
drugs. Dicyclopentadienyl titanium dichloride has been used for the treatment of lymphoid leukemia.
However, their anticancer activity is lower than those of cis platin and organotin compounds.
3. Surface treatment. Some titanium organic compounds especially titanium alkoxides are
easily synthesised by the reaction of TiCl4 with alcohols in the presence of ammonia or amines.
NH3
TiCl4 + 4ROH Ti(OR)4 + 4NH4Cl
Titanium
alkoxide
These alkoxides absorb moisture from air and get hydrolysed to form —Ti—O—Ti—O which
gives transparant film. Therefore, Ti(O—i Pr)4 is used for surface treatment for the prevention of
damage and scratching of glass. Ti(OBu)4 is used as heat resistant paint and can be used upto a
temperature of 600°C.
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172 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
4. Polymerization catalysts. Organotitanium compounds formed in situ from TiCl4 and AlR3
are used as polymerization catalysts for olefins as Ziegler – Natta type catalysts. The mixtures of
(C5H5)2 TiCl2. AlEt2 also catalyse polymerization reactions with same mechanism as TiCl3. AlEt2.
Mechanism of working of Ziegler Natta catalyst
A mixture of TiCl4 and triethyl aluminium in a hydrocarbon is known as Ziegler Natta Catalyst.
Ziegler Natta catalyst can be prepared by mixing TiCl 4 and Al2Et6 in heptane. A brown
suspension is obtained which readily
absorbs and polymerises ethene.
The mechanism of the function of
the catalyst involves the following steps:
(i) TiCl 4 and trialkyl aluminium
react to give fibrous form of TiCl 3 .
TiCl 3 consists of a hexagonal close
packed array of Cl– ions, with Ti3+ ions
occupying two-thirds of the octahedral
holes in each alternate pairs of layers.
(ii) The triethyl aluminium fils one
of the ethyl groups in the vacant site of Karl Zeigler G. Natta
Ti 3+ ion. Therefore, the catalyst has
octahedrally coordinated titanium atom at a surface coordinated to four chlorine atoms with another
site becoming vacant as shown.
Cl Ti Cl + Al Cl Ti + Al
Cl Cl Vacant site
Cl C2H5 Cl C2H5
(iii) The double bond in alkene molecule attaches itself to the vacant site on a Ti atom on the
surface of the catalyst finally forming a four centred transition state. This transition state enables
the ethyl group to transfer to coordinated ethylene. As a result, the carbon chain is extended (from
two to four in case of ethyl and ethene). As a result of migration, a coordinated site gets vacated.
CH3 CH3
CH2 Cl CH2 Cl
CH2 CH2
Cl Ti Cl Ti
CH2 CH2
Cl Cl
Cl Cl
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ORGANOMETALLIC CHEMISTRY 173
Cl Ti C Cl Ti CH2
Cl CH2
Cl Cl Cl
Preparation
1. Alkyl or aryl mercury compounds can be prepared from Grignard reagents.
RMgX + HgCl2 RHgCl + MgXCl
RHgCl + RMgX HgR2 + MgXCl
2. Disubstituted alkyls or aryls may be prepared by removing the mercury salt by reduction
or by conversion to very stable compounds as:
2C6H5HgI + 2Na (C6H5)2 Hg + Hg + 2NaI
Heat
(C6H5 Hg)2S (C6H5)2 Hg + HgS
2C6H5HgOAc + 2NaOH + Na2SnO2 (C6H5)2Hg + Hg + 2NaOAc + Na2SnO3 + H2O
2C2H5 Hg I + 2KCN (C6H5)2 Hg + K2HgI2 (CN)2
3. These can be obtained by direct replacement of hydrogen by mercury.
RH + HgX2 RHgX + HX
Ph H + Hg(OAc)2 Ph Hg OAc + HOAc
4. Organomercury compounds are prepared by the action of sodium amalgam on alkyl halide:
2RX + 2Hg Na / Hg HgR2 + HgX2
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174 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
Methylmercury iodide can be prepared by the direct combination of methyliodide and mercury
in the presence of sunlight although the reaction is very slow.
Sunlight
RI + Hg R HgI
(Slow)
5. The alkyls or aryls can be converted into organo mercury halides by treatment with the
halogens, halogen acids or mercuric halides. The reaction with mercury halide is given below.
R2 Hg + HgX2 2 R HgX
6. Organomercury compounds may also be synthesised using diazonium salts and alkyl lithiums.
Ar N2Cl + Hg Ar HgCl + N2
Diazonium salt
Hg
However, trimerisation takes place to maintain the linearity of C—Hg—C bond, as shown below
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ORGANOMETALLIC CHEMISTRY 175
Hg Hg
Hg
o-Phenylene trimer
6.14. FERROCENE*
The compound Fe(5 – C5H5)2 bis (cyclopentadienyl)
iron popularly known as ferrocene was discovered in 1951. It
has a sandwich structure in which the metal lies between two
planar cylopentadienyl rings. This compound has contributed
a lot towards the understanding of organometallic chemistry.
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176 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
Laboratory method
Ferrocene is prepared in the laboratory by treating iron (II) chloride with potassium
cyclopentadienide, which is obtained by the reaction of cyclopentadiene with caustic potash.
Cyclopentadiene which is used in the reaction normally gets dimersised at room temperature. It is
converted to monomeric state by heating to 180°C. The cracked product (monomeric
cyclopentadiene) which is obtained is kept in an ice both to prevent dimerisation again. The reactions
may be represented as
C5H6 + KOH C5H5K + H2O
Cyclopenta
diene
2 KC5H5 + FeCl2 (C5H5)2 Fe + 2KCl
Ferrocene
Properties of ferrocene
Physical properties. 1. It is an orange crystalline solid.
2. It is soluble in organic solvents like benzene but insoluble in water.
3. Its melting point is 174°C.
Chemical Properties
1. Acetylation. Ferrocene gives acetylation reactions with acetyl chloride in the presence of
anhydrous A1C13. Acetic anhydride in the presence of phosphoric acid can also be used.
This reaction occurs more readily with ferrocene than with benzene. Since the reaction
involves the electrophilic attack by the CH3CO+ group, therefore, it indicates that there is greater
availability of negative charge on the -cyclopentadienyl rings than on benzene ring.
O
—
— C — CH3
Anhydrous
AlCl3
Fe + CH3COCl Fe
Monosubstituted
derivative
O O
—
—
—
— C — CH3 — C — CH3
Anhydrous
Fe + CH3COCl Fe Disubstituted acetyl
AlCl3 derivative of ferrocene
— C — CH3
—
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ORGANOMETALLIC CHEMISTRY 177
2. Friedel Crafts alkylation. Ferrocene reacts with ethylene in the presence of anhydrous AlCl3
undergoing alkylation of the ring.
— CH2CH3
Anhydrous
Fe + C2H4 Fe
AlCl3
— CH2 — N(CH3)2
H
—
Fe + H — C — O + (CH3)2NH
— Fe
— HgOAc — HgOAc
CH OH
+ Hg(OAc)2 3
Fe Fe + Fe
— HgOAc
I2 I2
—I —I
Fe Fe
—I
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178 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
6. Nitration Ferrocene does not undergo direct nitration and halogenation reactions because
it gets oxidised to ferricinium ion, Fe (C2H5 )2+.
7. Reaction with alkyl lithium. Ferrocene reacts with n-buty lithium to give mono and
dilithium substituted products.
— Li — Li
n - BuLi n - BuLi
Fe Fe Fe
— Li
— NO2 — NH2
Fe Fe Fe
HCl
O4
N2
— Li — COOH
Fe (i) CO2 Fe
(ii) H2O
B(
Hy O
dro R)3 — B(OH)2 — HgCl
lys
is HgCl 2
Fe Fe
Cu
Br
2
Br2
— Br
Fe
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ORGANOMETALLIC CHEMISTRY 179
STRUCTURE OF FERROCENE
Ferrocene has a structure in which the iron atom is sandwiched between two C5H5 organic
rings. The planes of the rings are parallel so that all the carbon atoms are at the same distance from
the iron atom.
X-ray diffraction studies reveal that ferrocene has two types of arrangements of the
cyclopentadiene rings known as staggered or eclipsed. It has been observed that in gas phase the
structure of ferrocene is eclipsed while at low temperatures the structure of ferrocene is staggered.
The staggered configuration in the solid phase exists because of the crystal packing forces so that
carbon-carbon and hydrogen-hydrogen repulsions between the two rings are minimum. The energy
difference between staggered and eclipsed ferrocene configurations is only 4 kJ mol–l.
Fe Fe
Staggered Eclipsed
The bonding in ferrocene can be explained on the basis of valence bond theory and molecular orbital
theory as discussed below:
Valence bond theory. Valence bond theory does not provide satisfactory description of ferrocene
molecule, but it explains the diamagnetic character of a stable 18 electron outer configuration of the
molecule. The outer electronic configuration of Fe (II) is 3d 6 having six electrons in the 3d orbitals [Fig.
6.1 (a)]. To make available two d-orbitals for accommodating electron pairs from the ligands, the six
electrons get paired up in three orbitals [Fig. 6.1 (b)]. The six vacant orbitals (two 3d, one 4s and
three 4p) get hybridised forming six d 2sp3 hybrid orbitals which accept 12 electrons; 6 electrons from
each C5H5 ring. Thus, the molecule is diamagnetic as observed because there is no unpaired electron.
3d 4s 4p
(a) Fe (II)
2
d sp3 hybridisation
(b) Fe (C2H5)2
Molecular orbitals theory. The molecular orbital theory better explains the bonding in
ferrocene.
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180 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
The basic bond in ferrocene is a single bond between the -orbitals of C5H5 ring and the
iron atom. The bond is formed by the overlap of dxz and dyz +
orbitals on Fe (the z-axis is taken as the molecular axis) with
the delocalized p aromatic orbital from each pentadienyl
ring. + – +
2
The carbon atom involves sp hybridisation in pentadienyl
ring and forms three bonds (one with H atom and two with – + + –
neighbouring C atoms( Fig. 6.2). As a result, one p orbital is
left on each carbon atom containing one electron each. These five
– –
atomic orbitals now combine with one another to give five
molecular orbitals. These five MOs of ring can combine with Fig. 6.2. Cyclopentadienyl ring.
similar MOs of the second ring to form 10 molecular
+ –
orbitals called ligand group molecular orbitals. These
ligand group molecular orbitals combine with
appropriate orbitals having same symmetry of iron (five +
3d, one 4s and three 4p) to give molecular orbitals. – –
+
During their combinations 19 molecular orbitals are
formed, out of which 9 are bonding and 10 are
antibonding MOs. The ferrocene molecule has thus 18 +
–
electrons as:
8 from iron (3d 6 4s 2 ) + 2 × 5 fr om – +
cyclopentadiene rings = 18
These 18 electrons are arranged in the nine
bonding and non-bonding molecular orbitals. As a result + –
the 10 anti-bonding MOs remain vacant. –
In the ferrocene molecule, the most significant +
bonds are the bonds of symmetry formed between Fe
atom and the two C5H5 rings. These are obtained by the +
– –
overlap of d xz and d yz atomic orbitals of Fe with +
appropriate ligand group molecular orbitals of
cyclopentadiene rings. For example, the formation of a +
-bond between dxz orbital of Fe and the appropriate –
ligand group orbital is shown in Fig. 6.3. The interaction Fig. 6.3. The interaction between the ring
of the rings with dyz orbitals is similar. orbitals and the dxz orbital of the ion.
PtCl24 C2 H4
[PtCl3 (C2 H4 )] Cl
This was among the earliest olefin complexes prepared.
It was later discovered that certain metal halides or ions formed complexes when treated with
a variety of olefins.
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ORGANOMETALLIC CHEMISTRY 181
H H H H
C C
(a) – M + – M + M Alkene
Vacant d orbital
C
H H H H
Donation of electron density from filled MO of
ethylene to a vacant metal orbital.
H H
H H
+ C –
+ C –
– + – +
Alkene
(b) M M M
+ C –
+ – + –
+ C –
H H
H H Back bonding from a filled dorbital of
metal to vacant MO of ethylene.
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182 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
Pt
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ORGANOMETALLIC CHEMISTRY 183
Fig. 6.8 gives the structures of these complexes. In these structures, the two acetylenic carbons
are kept between the two cobalt atoms so that two -bonds of acetylene, which are perpendicular
to each other, interact with a cobalt atom.
Ph Ph
Ph Ph
C C C
C CO
Co Ni
CO Ni
Co
CO
CO....
CO CO
Catalyst
C=C + H2 —C—C—
H H
It is red violet compound having square planar geometry.
The mechanism of the reaction may be understood as follows: Geoffrey Wilkinson
(i) In the presence of hydrogen, RhCl (PPh3)3 solution forms octahedral dihydride compound.
Because of strong trans effect of H, it readily dissociates a molecule of Ph3P at room temperature
to give a five coordinate rhodium (III) species (compound II).
PPh3 H
H H PPh3
H2 –PPh3
RhCl (PPh3)3 Rh Rh H
PPh3 Cl Ph3P
PPh3 Cl
Octahedral Five co-ordinated
dihydride rhodium (III)
(I) (II)
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184 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
(ii) The species (II) combines with alkene molecule forming compound which has cis-
phosphines and ahydride trans to PPh 3 compound (III). This is a favoured product on steric
considerations.
H C C
PPh3 H H
Rh H + C C Rh
Ph3P Ph3P Cl
Cl
(III)
(iii) It gets labilized and transfers readily to alkene
to form an alkyl derivative (compound IV).
H C
M C
(IV)
Ph3P
Cl
C
(A)
–H transfer
H H
Ph3P reductive elimination Ph3P C
Rh — C Rh — C
Ph3P C—C Ph3P
– Cl
H H
(C) (B)
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ORGANOMETALLIC CHEMISTRY 185
The complete cycle for catalystic hydrogenation and isomerization of alkenes by RhHCO
(PPh3)3 at 25°C and 1 atm pressure is shown below.
The complex undergoes easier dissociation of PPh 3 ligand to form four coordinated
intermediate compound (II). The compound (II) then coordinates to an alkene (R—CH = CH2) to
form compound (III). The coordinated 1–alkene in (III) can react with a metal —H bond either by
Markownikoff addition or to form a secondary brranched alkyl derivative (IVb) or by anti-
Markownikoff addition to form a primary straight chain alkyl derivative (IVa). It may be noted that
an alkene–2 can give only a branched chain alkyl.
H H
Ph3P CH3 H
Rh — PPh3 C
Ph3P H
CO Rh
Ph3P
(I) CO
(IV b)
fast
+PPh3 –PPh3 (Markownikoff)
H H R
Ph3P R—CH = CH2 Ph3P CH
Rh Rh
Ph3P Ph3P CH2
CO CO
(II) (III)
fast
–CH3CH—R (anti-Markownikoff)
CH3—R
H
CH
Ph3P Ph3P + H2 PPh3
Rh Rh
slow
Ph3P CH2CH2R Ph3P
CO CO
(V) (IV a)
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186 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
M—H M—H
M—H + C C C C C C
H
C
H
M H
C
+ H2
M C Slow
C C
C – +
H H H
6.18. -ACIDITY
The ability of a ligand to accept electron density into vacant p-orbitals is called -acidity.
Complexes of metals with carbon monoxide are called metal carbonyls. Oxidation state of metal
in these complexes is either zero or a low positive value.
There are no attractive interactions between the metal and the ligands as is possible with the
positively charged metal ion. It is the main characteristic of CO ligand that it can stabilize low
oxidation states. This is due to the fact that it possesses vacant -orbitals in addition to lone pairs.
The formation of a sigma bond by the donation of a lone pair of electrons into the suitable vacant
metal orbitals leads to excessive negative charge on the metal (in zero or negative oxidation state).
To counter the accumulation of negative charge on the metal, -bond is formed by the back donation
of electrons from the filled metal orbitals into the vacant -type orbitals on the ligand. This also
supplements the -bond. This ability of the ligand (CO) to accept electron density into vacant
-orbitals is called -acidity. Therefore, CO is also called a p-acceptor ligand and the metal
carbonyls are referred as complexes of -acceptor (or acid) ligands.
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ORGANOMETALLIC CHEMISTRY 187
finely divided metal. For example, nickel carbonyl is prepared by the direct reaction of finely divided
nickel metal with CO at 25°C under one atmospheric pressure.
Ni + 4CO 25C
Ni(CO)4
Some other metal carbonyls require high temperatures and pressures.
For example,
200C
Fe + 5CO
Fe(CO)5
100 atm
200C
Mo + 6CO
Mo(CO)6
250 atm
2. Reduction. The metal salts are reduced in the presence of CO. For example,
AlCl
3 Cr(CO) AlCl
CrCl3 Al 6CO 6 3
C6 H6
150°C
2CoCO3 8CO 2H 2 Co2 (CO)8 2CO2 2H 2 O
250 atm
3 AlCl
WCl6 + 3Zn + 6CO W(CO)6 3ZnCl2
120°C
KOH, MeOH
Fe2 (CO)9 (Et4N)2 [Fe2 (CO)8]
Et 4 NI
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188 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
(b) Reduction of metal carbonyls with reducing agents produce carbonylate anions. The reduction
is carried out by alkali metal amalgams, hydride reagents and Na/K alloy in basic solvents including
liquid ammonia.
Na/Hg
Co 2 (CO)8
Na[Co(CO) 4 ]
THF
Na/Hg
Cr(CO) 6
Na 2 [Cr(CO)5 ]
THF
KH
Mn 2 (CO)8
2K[Mn(CO)5 ]
THF
(c) Many substituted carbonyl anions can be obtained by displacement of carbon monoxide
from a metal carbonyl.
Me4 NI + Mo (CO)6
Me4N [Mo (CO)5 I] + CO
Mo (CO)6 + NaB3H8
Na[Mo(CO)5 B3H8 ] + CO
(iv) Metal carbonylate anions can be prepared by the reaction with CH3 or C6H5 radicals.
–
O + OCH3
– H , CH2N2
(CO)5 Cr (CO) + CH3 (CO)5 Cr – C (CO5) Cr = C
CH3 – N2
CH3
3. Formation of cationic carbonyl complexes. These may be obtained in the formation of
complex halides by the reaction of carbon monoxide and a Lewis acid such as AlCl3 or BF3. For
example,
[Mn (CO)6 [A1Cl4]–
Mn (CO)5 Cl + CO + AlCl3
[Re (CO)6 ][AlCl4]–
Re (CO)5 Cl + AlCl3 + CO
(a) – M + + + C O; – M C O;
– Overlap
M C bond
– + + – – –
M + :C O: M :C O:
+ – – + + +
– Overlap
M C bond
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ORGANOMETALLIC CHEMISTRY 189
(ii) There is a -overlap involving donation of electrons from filled metal d-orbitals into vacant
antibonding molecular orbitals. This results into the formation of M CO bond. This is also
called back donation or back bonding. Fig. 6.9 (b)
The bonding in metal carbonyls is shown in Fig. 6.9. In these figures, the shaded orbitals repre-
sent filled orbitals.
The formation of dative bond tends to increase the electron density on the metal atom. At the
same time, the formation of bond from metal to carbon tends to decrease the electron density on
metal. Then the formation of bond increases the strength of M—CO bond. This accounts for the fact
that CO is a very weak Lewis base towards non-transition metal halides like BX3, AlX3, etc., but
forms very strong complexes with transition metals.
1 k
2
where is reduced mass of bonded atoms with mass m1 and m2 and is given as
m1 m2
m1 m2
The force constant is a measure of bond strength. Larger the force constant, stronger is the bond
and higher is the vibrational frequency. For example, a triple bond has higher force constant and therefore
higher frequency than a double bond (C C : 2200 cm –1 and C = C : 1650 cm –1). In infrared
spectrum the CO frequencies are generally very strong and, therefore, can be used to study the force
constant or bond strength of CO bond in different bonding situations.
Free CO has an infrared stretching frequency of 2143 cm–1. In the case of terminal carbonyl groups
in neutral molecules, the CO frequency has been found to be 2125-1850 cm–1. This suggests that the
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190 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
bond strength of CO has decreased or M—C bond strength has increased. This is only possible
if there is back bonding from filled metal d-orbitals to the antibonding orbitals of CO.
CO CO CO CO
OC CO OC
Cr Fe CO Ni
OC CO OC
OC CO
CO CO
Structures of some mononuclear carbonyls
CO CO CO CO
OC Mn Mn CO
CO CO CO CO
Structure of Mn2(CO)10
(ii) The binuclear carbonyls such as Fe2 (CO)9, Os2 (CO)9 and Co2 (CO)8 have bridging carbo-
nyl groups in addition to metal-metal bonds. Fe2 (CO)9 has three bridging CO groups placed sym-
metrically around the Fe—Fe bond. Each Fe atom is also bonded to three terminal CO groups.
Os2(CO)9 has only one bridging carbonyl group and each Os atom has four terminal CO groups.
We find that in addition to terminal CO groups, there are some bridging carbonyl groups in
dinuclear complexes. The bridging CO groups are symmetrical and have equal M—C distances.
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ORGANOMETALLIC CHEMISTRY 191
O O
OC C C
CO
(CO)4Os Os (CO)4
Fe Fe
OC C
CO O
C
CO O
CO Structure of Os (CO)9
Structure of Fe (CO)4
The bonding in bridging carbonyl groups may be regarded as 2-electron 3-centred overlap.
It may be noted that the bridge occurs over metal-metal bond. The carbon monoxide bridges in the
absence of metal-metal bonds are unstable. Thus, the metal-metal bond is essential for the stability
of the bridges. The stability to CO bridges depends upon the size of the metal atom. If the metal
atoms are larger in size, the bridged structures become unstable relative to unbridged structures.
Therefore, the relative stability of non-bridged structures increases as the size of the metal atom
increases. For example, the smaller Fe atom in Fe2(CO)9 has 3 bridging CO groups whereas bigger
osmium in Os2(CO)9 has one bridging CO group.
CO
CO
CO OC CO
CO M CO CO Fe
OC OC
CO CO
M CO Fe
CO
CO
CO OC CO Fe Fe
M
CO
CO
CO OC CO
CO
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192 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
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ORGANOMETALLIC CHEMISTRY 193
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194 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
– CO C5H5N
(v) Mo(CO)6 + C5H5N C5H5NMo (CO)5 (C5H5N)2 Mo(CO)4
– CO
C5H5N(– CO)
(C5H5N)3 Mo(CO)3
EXERCISES
(Including Questions from Different University Papers)
Multiple Choice Questions (Choose the correct option)
1. Out of Cr(CO)6 (A) and [Ag(NH3)2]+ (B)
(a) (A) obeys EAN rule and (B) does not
(b) (B) obeys EAN rule and (A) does not
(c) (A) and (B) both obey EAN rule
(d) Neither (A) nor (B) obeys EAN rule
2. Which of the following organometalic compound does not obey EAN rule ?
(a) Co(CO)3 (-C3H5) (b) (C2H5) Cr(CO)3 (-C5H5)
(c) [Mn(CO)5 (C2H4)]+ (d) Co(C6H6)2.
3. An example of olefin complex is
(a) Ferrocene (b) Zeise salt
6
(c) Bis ( -benzene) chromium (d) (CO)6 Co2 (PhC CPh).
4. Which of the following has lowest CO stretching frequency ?
(a) Ni(CO)4 (b) [V(CO)6]+
(c) [Co(CO)4]– (d) [Fe(CO)4]2–.
5. Which of the following will have highest CO stretching frequency ?
(a) Cr(CO)6 (b) Mn(CO)6+
(c) V(CO)6 (d) Fe(CO)42–.
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ORGANOMETALLIC CHEMISTRY 195
ANSWERS
1. (a) 2. (d) 3. (b) 4. (d) 5. (b) 6. (c)
7. (a) 8. (a) 9. (d) 10. (b) 11. (c) 12. (d)
13. (c) 14. (c)
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196 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
General Questions
1. Carbon monoxide is considered to be a special type of ligand in organometallic compounds.
What is so special about carbon monoxide in these compounds ?
2. Name the different categories of organometallic compounds. Discuss with one example each.
3. What are organometallic compounds ? Give structures of organometallic compounds formed
by 5, 6 and 8 electron donor unsaturated molecules.
4. Give IUPAC names of the following:
(i) (C6H6) Cr(CO)3 (ii) Fe(C5H5)2
(iii) (–C5H5)2 Ti(-C5H5)2 (iv) ReH (-C5H5)
5. What is EAN rule ? Give two examples each of organometallic compounds in which EAN
rule is (i) obeyed and (ii) not obeyed.
6. What are metal olefin complexes ? Give one method for the preparation of an important
metal olefin complex. Discuss the bonding in these complexes.
7. What are organotin compounds ? Discuss their preparations structures and applications.
8. (a) What is a ligand ? How are the ligands classified ? Give one example in each case.
(b) Give a brief account of homogeneous hydrogenation catalysts.
9. (a) Discuss bonding in metal carbonyls. How does infrared spectroscopy help in explaining
bonding in metal carbonyls ?
(b) Can infrared spectroscopy distinguish between the terminal and bridging CO groups in
metal carbonyls ? Explain.
10. What are metal-alkyne complexes ? Discuss the different types of bonding in these
complexes with or example of each.
11. Define organometallic compound. Give structures of complexes in which cycloctatetraene
behave as 4-electron donor, 6-electron donor and 8-electron donor.
12. Calculate the EAN value for each of the following species :
(a) Cr(C5H5) (CO)3 (b) Fe(– C5H5) (CO)3
(c) (– C3H5) Mo(CO)3 (C5H5) (d) (Me3Si) W(CO)3 (– C5H5)
(e) Co(– C5H5)(CH3)2
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ORGANOMETALLIC CHEMISTRY 197
13. What are organometallic compounds. Give IUPAC names of the following :
(a) Ni (– C5H5)2 (b) (CO)5 Mn – Mn(CO)5
(c) Ru (CO)3 (C4H6) (d) [PtCl3 (C2H4)]–
(e) Co (CO)3 (– C3H5)
14. Write formulae for the following organometallic compounds
(a) (3 - allyl) tricarbonyl cobalt
(b) (1 - allyl) tricarbonyl (5 - cyclopentadienyl) molybdenum
(c) Bis (5 - cyclopentadienyl) iron
(d) Tricarbonyl (5 - cyclopentadienyl) manganese
(e) (4 - butadiene) tricarbonyl iron
15. (a) Give one method for the preparation of each of the following :
(i) Ni(CO)4 (ii) Fe2(CO)9 (iii) Co2(CO)8 (iv) Fe(CO)5
(b) Draw structures of the above metal carbonyls.
16. Discuss the structures of the following compounds :
(a) Mn2(CO)10 (b) (5- C5H5) Mn(CO)2 (Ph2C2)
(c) K[PtCl3 (C2H4)] (d) Fe3(CO)12
(e) Co2(CO)8 solid
17. (a) What are metal carbonyls ? Discuss a method of preparation and structure of one
(i) mononuclear (ii) dinuclear and (iii) trinuclear carbonyl.
(b) Discuss the bonding in metal carbonyls and evidence in support of such bonding.
18. (a) What are metal carbonyls ? Give structures of two dinuclear metal carbonyls having
different structures.
(b) How does infrared spectroscopy help in explaining the bonding in metal carbonyls ?
19. (a) What is Zeise salt ? Draw its structure and discuss the salient features of this structure.
(b) Give an example where an alkyne behaves as a bidentate divalent ligand.
20. (a) How is dicobalt decarbonyl prepared ? Discuss its structure.
(b) How does infrared spectroscopy help in explaining the type of metal–CO group bonding
in the complex ?
21. Complete the chemical equations :
FeO + 2C5H6 523K
Fe + 2C5H6 573K
22. (a) Discuss the nature of bonding in metal olefin complexes.
(b) Discuss the structures of
(i) Os2 (CO)9 (ii) Ni (CO)4
23. (a) Discuss the nature of bonding in metal-olefin complexes.
(b) Explain the structures of
(i) Mn2(CO)10 (ii) Fe (CO)5 (iii) Ni (CO)4 (iv) Fe3 (CO)12.
24. (a) N2 is isoelectronic with CO, it is a poor donor than CO. Explain.
(b) Draw the structures of the following :
(i) Co2 (CO)6 . (Ph2C2) and (ii) Fe3 (CO)12.
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198 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
25. (a) Discuss the nature of bonding in metal carbonyls. Give experimental supports in its
favour.
(b) Cyclopentadiene ring in ferrocene show aromatic character but cyclopentadiene itself
has no such aromatic character.
(c) Why can lower oxidation states exist in metal complexes of CO, NO, etc.
26. In case of transition metal carbonyls state:
(i) Whether the metals are in their lower oxidation states or not?
(ii) EAN rule is obeyed or not?
(b) Define acidity and give one example.
(c) Describe the structures of V(CO)6, Ni (CO)4, Mn2(CO)10, Fe2(CO)9, Os2(CO)9, and
Co(CO)8
27. (a) Draw the structure of Fe2 (CO)9.
(b) Complete the following equations giving only the major products :
(i) Fe(C5H5)2 + HCHO + HN(CH3)2
Na / Hg
(ii) Co2(CO)8
THF
(iii) K2PtCl4 + C2H2
(iv) Mo(CO)6 + Pyridine
(v) KC5H5 + FeCl2
(vi) (C5H5)2 Fe + Li C4H9
28. What do you understand by -elimination in transition metal alkyls ? How can it be avoided ?
Explain giving examples.
29. (a) What is EAN rule ? Show whether the compounds Cr(CO)6, Ni(PF3)4 and Fe(CO)4
(PPh3) obey the EAN rule.
(b) Complete the following reactions :
Na / Hg
(i) Co2(CO)8
THF
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ORGANOMETALLIC CHEMISTRY 199
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200 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
Na OO CCH3 ; Mn (C5H5)2;
CH3Sn H2Cl ; (H5C6)3 Si–Si (C6H5)3
(c) What is the use of IR spectroscopy in the elucidation of structure of meal carbonyls ?
42. (a) Discuss briefly bonding in metal-alkyne complexes.
(b) Give IUPAC name of the following compounds :
(i) Ni (–C5H5)2
(ii) (CO)5 – Mn–Mn (CO)5
(iii) Ru (CO)3 (C4H6)
(c) Calculate EAN vlaue for the following :
(i) Cr (C5H5) (CO)3
(ii) Fe (–C5H5) (CO)3
43. (a) Discuss the structure of (LiCH3)4.
(b) Give important industrial applications of organotin compounds.
(c) Briefly discuss the metal-carbon sigma bonding.
44. (a) Complete the reactions :
(i) Co2(CO)8 Na / Hg, THF
(ii) K2PtCl4 + C2H2
(iii) Fe(CO)5 + NaOH
(b) Why do organolithium compounds prefer to oligomerize than exists as single molecule ?
(c) Discuss structure of Fe2(CO)9.
(d) Write names of following organometallic compounds
[(CO)3Fe(CO3)Fe(CO)3] ; [Fe(-C5H5)2] ; [Cr(C6H6)2]
45. (a) Discuss the nature of bonding in metal-olefin complexes.
(b) “Both N2 and CO are isoelectronic, yet N2 is a poorer donor than CO”. Explain.
(c) What are metal carbonyls ? Discuss the structure of V (CO)6 and Fe (CO)5.
46. (a) Discuss bonding in metal carbonyl complexes.
(b) Complete the reactions :
Na / Hg
(i) Co2 (CO)8
THF
(ii) K2PtCl4 + C2H2
(c) Discuss the structure of Fe2(CO)9.
(d) Give mechanism of homogeneous hydrogenation of alkenes with Wilkinson catalyst.
(e) Give structure of Zeise salt.
47. (a) Discuss preparation, properties, bonding and applications of organoaluminium
compounds.
(b) What do you mean by homogeneous hydrogenation ? Name three homogeneous catalysts
used for homogeneous hydrogenation of alkenes.
48. (a) Discuss important applications of organoaluminium compounds.
(b) Give two important methods of preparation of metal carbonyls.
(c) Briefly discuss the structure of binuclear metal carbonyls.
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ORGANOMETALLIC CHEMISTRY 201
49. (a) Describe bonding in metal carbonyls. How does IR spectroscopy help in explaining
bonding in metal carbonyls ?
(b) Give methods of preparation of the transition metal carbonyls.
(c) Give one method of preparation of metal alkene complex. Also explain bonding in this
complex.
50. (a) In which of the following complexes EAN rule is objected ?
(i) [Mn(CO)5C2H4]+ (ii) [Mo(CO6)]
(iii) [Cu(NH3)4] (iv) [Co(CO)4]
(b) Give two examples which would distinguish between organometallic and non-
organometallic compounds.
(c) Discuss nature of bonding in metal carbyne complexes.
(d) Write formulae against the names of the following organometallic compounds :
(i) Hexacarbonyl niobate (–1)
(ii) Tetracarbonyl bis (ethylene) manganese (+1).
51. (a) Discuss the bonding in metal-carbonyl complexes. How IR spectra helps in explaining
bonding in metal-carbonyls ?
(b) How homogeneous hydrogenation of C2H4 is carried out by using Wilkinson’s catalyst ?
(c) Define metal carbonyls. Draw the structures of :
(i) Ni(CO)4 (ii) Fe(CO)5
(iii) Cr(CO)6 (iv) Mn2(CO)10
52. (a) Classify bonding in organometallic compounds. Give examples of each type.
(b) What do you understand by -elimination in transition metal alkyls ? How can it be
avoided ?
(c) Why do organolithium compounds prefer to doligomerize rather than exist as single
molecule ?
53. (a) Discuss the synthesis and bonding of Zeise salt.
(b) Write the nomenclature of the following compounds :
(i) PtCl3 (2 – C2H4)–
(ii) Mn (3 – C3H5) (CO)4
(iii) Rh (CO) Cl (PPh3)2
(c) Define haptacity and discuss the classification of organometallic compounds on the basis
of haptacity.
54. (a) Write the IUPAC names of the following :
(i) Zn (C2H5)2
(ii) CH3–SnH2Cl
(iii) Fe (5 – C5H5)
(iv) [Mn (3 – C6H5) (CO)4]
(b) How sepectroscopical evidences support bonding in metal carbonyls ? Explain.
55. (a) Discuss the nature of bonding in metal carbonyl.
(b) Discuss transmetallation for the synthesis of organometallic compounds.
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202 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)
56. (a) Define EAN rule. Which of the following species obey effective atomic number rule and
why ?
(i) Co (CO)4 (ii) H3C Mn (CO)5
(iii) Fe (CO)3 (C4H6) (iv) Fe (-C5H5)2
(b) What do you understand by beta-elimination in transition metal-alkyls ? How can it be
avoided ? Give examples.
(c) Discuss and draw the structure of Zeise’s salt ?
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