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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.

6.2. DEFINITION OF ORGANOMETALLIC COMPOUNDS


Organometallic compounds are the compounds which contain one or more metal-carbon
linkage. For example, tetraethyl lead, ziese salt, diethyl zinc, ferrocene, etc.

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.

6.3. DIFFERENT TYPES OF ORGANOMETALLIC COMPOUNDS


Theorganometallic compounds may be classified into the following types depending upon the
nature of metal-carbon bond.
1. Ionic compound. Such compounds are formed when the negative charge on the hydrocarbon
anion is delocalised over carbon atoms in the aromatic or unsaturated ring. K+ C5H5– is a common
example of this type where delocalisation of negative charge over the five carbon atoms of
cyclopentadienyl ring gives rise to a stable complex. Some other examples of such compounds are:
butyl sodium, Na + C4H9– phenyl sodium, Na + C 6H5– trityl sodium, Na + (C6H5) 3 C–. These
compounds exhibit properties expected from ionic compounds. They are insoluble in non-polar
solvents. The reactivity of ionic organometallic compound depends upon the stability of the anion.
Compounds containing unstable anions are found to be extremely reactive.
2. Covalent compounds. Such compounds have the metal bonded to an organic part by normal
two-electron sigma covalent bonds. Such compounds give properties expected from covalent
compounds. They are soluble in organic solvents and insoluble in water. Electronegativity difference
between the metal atom and carbon determines the polarity of the carbon-metal bond.
Common examples of this type of compounds are:
Pb (C2 H5)2 , (CH3)2 Cd, (C6 H5)2 Zn, (CH3)3 Al
3. Electron deficient compounds. Formation of this type of compounds cannot be explained
on the basis of formation of usual two electrons–two
centre bonds with carbon and metal atom. Compounds H H H
of Li, Be, Mg and Al with bridging alkyl groups C
appear in this category of compounds. Dimeric CH3 CH3
trialkyl aluminium (Al 2 R6), polymeric dimethyl
Al Al
beryllium (Be Me2)n and diethyl magnesium (Mg
CH3 CH3
Et2)n are some examples of this type of compounds.
These compounds possess high charge to mass ratio C
and thus have strongly polarizing cation. As a result,
H H H
polar covalent bond results.
Such polar molecules tend to associate and give Fig. 6.1. Structure of dimeric Al2Me6.
polymeric structures. Trialkyl aluminium exists as
dimeric in which the alkyl group is present as bridge (Fig. 6.1).
4. Transition metal organometallic compounds. These organometallic compounds have
transition metals bonded to unsaturated organic compounds in
which the transition metal forms bonds to more than one
carbon atoms of the same organic compound. The interaction
occurs between the p-orbitals of the organic ligands with the
suitable d or p orbitals of the metal atom.
The common examples of ligands forming such type of Cr Fe
organometallic compounds are (i) alkene (2-electron donors),
(ii) butadiene (4-electron donors), (iii) cyclopentadiene
(5-electron donors) and (iv) benzene ring (6-electron donors).
The common structures of dibenzene chromium (C6H6)2Cr and
ferrocene (C5H5)2 Fe are shown in Fig. 6.2. Their structures are Fig. 6.2. Structures of (a) (C H ) Cr
6 6 2
known as sandwich structures in which metal atom lies in and (b) (C5 H5)2 Fe.
between two rings.

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150 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

6.4. CLASSIFICATION OF THE LIGANDS


An atom, ion or molecule which is capable of donating a pair of electrons to the metal atom is
called a ligand. The number of atoms of the ligand which are within bonding distance of the metal atom
is called its hapticity. It is written by using the symbol (eta).
The ligands are classified on the basis of number of carbon atoms involved in bonding to the metal
atom, i.e., hapticity. The hapticity ranges from 1 to 8.
1. One carbon bonded ligands. These are the molecules in which the carbon atom of the ligand
is bonded directly to the metal atom. Such ligands are also called monohapto ligands (one electron
donors), . For example, –CH3 group attaches by a single M – C bond. These ligands are of the
following different types:
(i) Hydrocarbon ligands. These include alkyl (–CH3), aryl (– C6H5), (– CR = CR2), -cyclop-
entadienyl (–C5H5), alkynyl ( – C  CR) group.
For example, cyclopentadiene, C5H5, combines with alkali metals to form ( – C5 H5) M
compound as shown below:
H M

(One carbon bonded cyclopentadienyl compound).


(ii) Acyl ligands. These ligands include acyl group which involves direct bonding of the acyl
group (–COR) to a metal atom as shown below:
O O

— —

— C— M — C—
R R
Acyl group Organometallic
compound
These compounds are formed by transition metals only.
(iii) Carbene ligands. These ligands involve the direct metal carbon-bond of the carbon atom
of carbene (alkylidene) to a metal atom.
R R
— —
  C — M  : C—
R R
Carbene ligand Organometallic
compound

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

Benzene as hexahapto ligand Dibenzene chromium (C6H6)2Cr

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.

Cyclo-octatetraene (C8 H8) Dicyclo-octatetraeneuranium


Cyclooctatetraene can also act as four electron donor, for example in Fe(CO)3 and as six-
electron donor, for example in Mo(CO)3

Fe(CO)3 Mo(CO)3
Cyclooctatetraene Cyclooctatetraene
4–electron donor (6–electron donor)

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ORGANOMETALLIC CHEMISTRY 153

6.5. EFFECTIVE ATOMIC NUMBER RULE


Sidgwick suggested that metal ion accepts electron pairs from the ligands until it achieves
the next noble gas configuration. This is called effective atomic number rule. The total
number of electrons possessed by the central metal ion and the electrons gained by it from
ligands is called the effective atomic number (EAN). Thus, according to effective atomic
number rule, the effective atomic number in a complex should be equal to 36 (electrons in Kr),
54 (electrons in Xe) and 86 (electrons in radon).
The rule may be illustrated by taking the following examples:
(i) Hexaammine Cobalt (III) ion, [Co(NH3)6]3+
Atomic number of Co = 27
Electrons in Co(III) = 24
Six ammonia molecules give two electrons each (6 × 2) = 12
Total number of electrons in the ion (EAN) = 24 + 12 = 36
Thus, the complex obeys EAN rule.
(ii) Tetracarbonyl nickel (0), Ni(CO)4
Atomic number of Ni = 28
Electrons in Ni(0) in Ni(CO)4 = 28
Four CO groups give two electrons each (4 × 2) =8
EAN of [Ni(CO)4] = 36
Thus, the complex [Ni(CO)4] obeys EAN rule.
(ii) Pentacarbonyl iron (0), Fe(CO)5
Atomic number of Fe = 26
Electrons in Fe(0) = 26
Five CO groups give two electrons each (5 × 2) = 10
EAN = 36
Table 6.1 gives the list of some other complexes obeying EAN rule.
Table 6.1 Complexes obeying effective atomic number rule.
Complex Central At. No. No. of electrons in Electrons EAN
metal ion metal ion ligands gained from
[Fe(CN)6]4– Fe2+ 26 24 12 36 (Kr)
[Fe(CO)5] Fe 26 26 10 36 (Kr)
[Cr(CO)6] Cr 24 24 12 36 (Kr)
[Ni(CO)4] Ni 28 28 8 36 (Kr)
[Pt(NH3)6]4+ Pt 4+ 78 74 12 86 (Rn)
[PtCl6]2– Pt 4+ 78 74 12 86 (Rn)
[Pd(NH3)6]4+ Pd4+ 46 42 12 54 (Xe)
Table 6.2 gives the list of metal carbonyls obeying EAN rule.

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Table 6.2 Metal carbonyls obeying EAN rule.


Electrons in Electrons donated
Complex Metal ion Metal ion from ligands EAN
Cr(CO)6 Cr 24 12 36
Fe(CO)5 Fe 26 10 36
Ni(CO)4 Ni 28 8 36
Mo(CO)6 Mo 42 12 54
Ru(CO)5 Ru 44 10 54
Os(CO)6 Os 76 10 86
W(CO)6 W 74 12 86
But we observe that EAN rule is not obeyed in many stable complexes.
Table 6.3 gives the list of such complexes.
Table 6.3 Complexes not obeying effective atomic number rule.
Complex Central At. No. No. of electrons in Electrons EAN
metal ion metal ion ligands gained from
[Ni(CN)4]2– Ni2+ 28 28–2 = 26 8 34
[Ni(NH3)6]2+ Ni2+ 28 28–2 = 26 12 38
[Pt(NH3)4]2+ Pt2+ 78 78–2 = 76 8 84
[Fe(CN)6]3– Fe3+ 26 26–3 = 23 12 35
[Cr(NH3)6]3+ Cr3+ 24 24–3 = 21 12 33
[Ag(NH3)2]+ Ag + 47 47–1 = 46 4 50
[PdCl4]2– Pd2+ 46 46–2 = 44 8 52
EAN rule can explain the stability of metal carbonyls but it cannot be the sole criteria to form
stable carbonyls. Metals with odd number of electrons cannot obey EAN rule because total number
of electrons will always be odd, no matter how many carbonyls are added. Thus, hexacarbonyl
vanadium V (CO)6 is a stable complex though it does not obey EAN rule as:
Atomic No. of V = 23
Electrons in V(0) = 23
6 CO groups give two electrons each (6 ×2) = 12
EAN = 35
Therefore, the complex V (CO)6 does not obey EAN rule.
In order to satisfy EAN rule, there are some options for the metal
ions. These are:

(i) They may form carbonylate anion such as [M(CO)n] by gaining
an electron from a reducing agent or they may form cationic species,
[M (COn)] + by losing an electron. For example, the anions
– – – Henry Sidgwick
[V (CO)6 ] , [Mn(CO)5 ] , [Co (CO)4] obey EAN rule.

[V (CO)6]
Atomic number of V = 23

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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

6.6. NOMENCLATURE OF ORGANOMETALLIC COMPOUNDS


The rules for the nomenclature of coordination compounds have been explained in the previous
class. Most of these rules apply to organometallic compounds. However, some of the rules are
modified keeping in view the complex nature of the ligands.
Nomenclature of different types of organometallics is discussed as under.
1. Nomenclature of simple compounds. The simple alkyl or aryl organometallic compounds
of metals are named by writing the name of the metal after the name of organic group. For example,
CH3 Li Methyl lithium
(C2 H5 )2 Zn Diethyl zinc
C2 H5 MgBr Ethyl magnesium bromide
C6 H5 MgC1 Phenyl magnesium chloride
2. Nomenclature of carbonyls. (i) The compounds containing CO as ligands are called metal
carbonyls. In case the metal has zero oxidation state, it may not be mentioned.
For example,
Ni (CO)4 Tetracarbonylnickel
Mn2 (CO)10 Decacarbonyldimanganese
Fe2 (CO)9 Nonacarbonyldiiron

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ORGANOMETALLIC CHEMISTRY 157

Co2 (CO)8 Octacarbonyldicobalt



[V(CO)6] Hexacarbonylvanadate ion
(ii) If the ligands act as bridges between two metal atoms, the Greek letter mu () is written
before their names. The prefix is repeated before the name of each kind of bridging ligand. For
example,
[ (CO)3 Co (CO)2 Co (CO)3 ] Di--carbonyl bis (tricarbonyl cobalt)
[ (CO)3 Fe(CO)3 Fe (CO)3 ] Tri-carbonyl bis (tricarbonyl iron)
(iii) When the metal carbonyls contain metal-metal bonds, these may be classified as symmetrical or
unsymmetrical. The symmetrical metal carbonyls are named by the use of multiple prefixes (bis, tris,
etc.). In case of unsymmetrical metal carbonyls, one central metal atom and its ligands are treated as a
ligand on the other central metal atom. For example,
[(CO)4 Co – Co (CO)4] Bis (tetracarbonylcobalt)
(symmetrical)
[(CO)4 Co – Re (CO)5] Pentacarbonyl (tetracarbonyl cobalto) rhenium
(unsymmetrical)
3. Nomenclature of  and  bonded ligands. We use the notations  and  to distinguish
between one carbon bonded ligand and multiple carbon bonded ligands. For example, cyclopentadiene
(C5H5 ) is referred to as  – C5H5 (e.g., Li C5H5 ) when it behaves as one carbon bonded ligand.
However, when it behaves as five carbon bonded ligand, it is named as -C5H5 (e.g.
 (C5H5 )2 Fe). Similarly, alkyl group is referred as -ally1 or ally1 depending upon whether it
behaves as one electron donor or three-electron donor.
For unsaturated molecules or groups, the prefix  (called as eta or hapto) is used. For example, a one
carbon bonded ligand is specified by monohapto (or  ), two carbon bonded ligand as dihapto (or
2), three carbon bonded ligand as trihapto (or 3 ), a four carbon bonded ligand as tetrahapto (or 4 )
and so on. According to latest IUPAC convention, the  notation is recommended.
For example,
Fe (C5H5)2 Bis (5-cyclopentadienyl) iron
Cr (C6 H6)2 Bis (6-benzene) chromium
Co (CO)3(– C3H5) (-ally1) tricarbonyl cobalt
(C6H6 ) Cr (CO)3 (-benzene) tricarbonyl chromium
Fe2 (CO)4 (C5 H5 )2 Bis (5-cyclopentadienyl) tetracarbonyldiiron
Fe (CO)2 ( – C5H5 )( – C5H5) Dicarbonyl (-cyclopentadienyl)
(-cyclopentadienyl) iron
Fe (CO)3 (C4 H6) (4-butadiene) tricarbonyl iron
Mn (CO)5 (– CH2 – CH = CH2 ) (-ally1) tricarbonyl iron

6.7. BONDING IN ORGANOMETALLIC COMPOUNDS


The type of bonding in an organometallic compound determines its properties. The different
types of bonding that occur in an organometallic compound are 1. Ionic bonding. 2. -covalent
bonding. 3. Multiple covalent bonding.

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158 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

These are separately discussed as under:


1. Ionic bonding. This type of bonding is observed in organometallic compounds of
electropositive metals like sodium, potassium, rubidium, cesium, magnesium etc. In such compounds,
the hydrocarbon contains carbon carrying negative charge which is strongly attracted by the positively
charged metal ion by electrostatic forces of attraction. In some cases, the negative charge is
delocalised over the ring containing different number of carbon atoms. For example, in
Mg2+ (C5H5–)2, the negative charge of cyclopentadienide anion, C5H5–, is delocalised over the ring
of five carbon atoms.
2. -covalent bonding. This type of bonding occurs in organometallic compounds of
representative elements. It is generally observed in metal-alkyl bonds. For example, (CH3 )4
Sn, C4H9 Li, (CH3)6 Al2, etc. The polarity of covalent bond between metal and alkyl group depends
upon the difference in electronegativity between metal atom and carbon atom.
Transition metals can also form metal-carbon  bonds with organic groups although relatively
unstable. They can easily decompose even at room temperature. For example, the alkyl derivatives
of transition metals such as Ti (CH3)4, Nb CH3)5, W (CH3)2 are well known but they are unstable
and explode even below room temperature. The stability of the -bonded covalent compounds
increases if some additional -bonding ligands are also present. For example, the presence of ligands
such as PR3, CO, amines, etc. increases the stability of these compounds. For example, tetramethyl
titanium undergoes spontaneous decomposition violently at –23° C but the addition of dipyridine
or diamine increases its stability and it does not decompose up to room temperature.

6.7.1. Factors responsible for kinetic instability of transition metal sigma


bonded organometallic compounds
The following factors contribute to kinetic instability of organometallic compounds containing
metal-alkyl bond:
(i) Formation of reactive species due to cleavage. The cleavage of metal-carbon bond in
transition metal alkyls give reactive alkyl radicals or ions. The reactive species formed react with
each other or solvent to give chain reactions. This behaviour is different from that of the other
inorganic metal-ligand bonds such as M– OH2, M –NR2, M – X (X = halogen), etc. where a
cleavage leads to relatively less reactive species like H2O, R2N– or X– respectively.
(ii) Cleavage products form strong bonds. In case the cleavage of metal-carbon bond occurs,
they combine among themselves to form strong bonds such as C—C, C—O, C—N, C—X (X =
halogen) etc. depending upon the nature of organometallic compound. During the formation of new
bonds, the cleavage reaction is highly exothermic and is thermodynamically favoured. For example,
metal-alkyl bond undergoes cleavage as
 
M — R 
 M + R

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

6.7.2. Factors that can increase stability of metal-alkyl compounds


The following measures can increase stability of metal-alkyl compounds.
(i) Chacking -elimination. In higher alkyl organometallic OMe R
compounds, the hydrogen present on carbon atom at -position
to the metal is labile (removable). It brings about decomposition C
of the compound into metal hydride and an alkene. This is called OC OC
-elimination.
The -elimination is responsible for the instability of alkyl W
organometallic compounds. Therefore the blockage of
-elimination reaction can bring about stability in metal alkyls. CO CO
Alkyls which do not contain replaceable hydrogen atom on
CO
-carbon are therefore stable. For example,
Structure of (CO)5WCR (OMe).
M – CH2 – CH3, M – CH2 – Ar, M – CH2 – NR2 etc.
(ii) Chelation. The stability of a metal-carbon sigma bond can be enhanced by chelation.
Donation through a terminal group can bring about chelation.
(iii) Increase in coordination number. The stability of metal-alkyl compound can be raised
  

by delocalising the negative charge on carbon M — C . Thus aromatic compounds having metal-
carbon linkage are relatively more stable. For example M—C6H5 is more stable than M—CH3.

6.8. METAL-CARBON MULTIPLE BONDING


If multiple bonding occurs between metal and carbon, the bond strength is increased. For
example, carbenes, = CR2 and carbynes,  CR form double and triple bonds with the metal atom.
CR It hasbeen observed that in carbene compounds, the
metal-carbon bond is somewhat shorter than normal
OC CO metal-alkyl  bond but larger than metal-carbon
double bond. This suggests that the bond between
metal-carbon in carbenes is in between single and
M double bond.
The first carbene
OC CO complex (CO) 5
W[ : C(R) OMe)] was
synthesised by Emil.
X Fisher in 1964. It has
Structure of (CO)4 M (=CR)X been found to have
octahedral arrangement with one of the positions occupied by the
carbene, = CR (OMe).
Metal carbynes have triple bonds. For example, (CO)4 M (  CR)X
where M = Cr, Mo or W, R = Me, Et or Ph, X = CI, Br, I). The crystal
structure of these types of complexes shows that  CR group occupies
position trans to halo ligand in an octahedral geometry. Emil Fischer

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160 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

6.9. ORGANOLITHIUM COMPOUNDS


Organolithium compounds are versatile reagents to achieve synthesis of a wide variety of
inorganic and organic compounds. These compounds are particularly used as alkylating reagents.
These compounds are generally polymeric in nature and are soluble in hydrocarbon solvents.
Preparation
Organolithium compounds can be prepared as follows:
1. By direct reaction of Li with alkyl or arylchloride in benzene or petroleum.
Solvent
2Li + RCI   LiR + LiC1 (R = alkyl or aryl)
Solvent
2Li + C2H5C1   C2 H5 Li + LiCl
2. By metal-halogen exchange in ether. Lithium aryls are best prepared by this method using n-
butyl lithium and an aryl iodide.
Ether
n – C4 H9 Li + ArI   LiAr + n-C4 H9 I (Ar = aryl)
Br Li
Ether
n – C4H9Li + + n – C4H9Br
N N
3. Vinyl-allyl and other unsaturated derivatives can be obtained by transmetallation.
Ether
4Li Ph + Sn (CH = CH2)4   4LiCH = CH2 + SnPh4
4. Methyllithium is also prepared by exchange through the interaction of n–C4 H9 Li and CH3I
in hexane at low temperatures where it precipitates as insoluble white crystals.
hexane
n – C4 H9 Li + CH3 I   CH3 Li + n – C4 H9 I

5. By metal-hydrogen exchange (metallation) in ether.


Et2O
LiPh + Li + C6H6 (Ph = phenyl)

Furan Furan lithium

Li

n – C6H9Li + Fe Ether Fe + n – C4H10

6. By deprotonation of alkynes in liquid ammonia solution. Lithium acetylides and dicarbides


are obtained by this method using Li metal and acetylene. For example,
Liq. NH3
Li + HC CH   LiC CH + 1/2 H2
Liq. NH3
2Li + HC  CH   Li2 C2 + H2
7. By metal-metal exchange in petroleum or benzene. Reaction between an excess of Li and an
organomercury compound is a useful alternative when isolation of the product is required, rather
than its direct use in further synthetic work. For example,
Petrol or
2Li + Hg R2   2LiR + Hg
benzene

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ORGANOMETALLIC CHEMISTRY 161

Properties. 1. Organolithium compounds tend to be thermally unstable and most of them


decompose to LiH and an alkene on standing at room temperature or above.
2. They are generally liquids or low melting solids and are found in molecular association.
3. Organolithium compounds are typical covalent substances, soluble in hydrocarbons or other
non-polar liquids.
4. They react rapidly with oxygen and are usually spontaneously flammable in air, with liquid
water and with water vapours.
5. LiMe and LiBu are usually synthetic reagents and have been increasingly used in organic
syntheses as polymerization catalysts, alkylating agents and precursors to metalated organic reagents.
Some of the reactions with different compounds are given below:
(a) Reactions with alkyl iodides give compounds having C – C bonds. For example,

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

Li+ + R — C — H + [(Solvent) Ni (CO)3]


Aldehyde
O H+ ent
lv

So
Li+ [R — C — Ni (CO)3] –
R
B r O
So



lv
en

LiBr + R — C — R + [(Solvent) Ni (CO)3]


t

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 + Ar2 LO  H 2O
 [Ar2 C (Ar) OLi]   LiOH + Ar
Ar 2 C (Ar) OH

(i) Reactions with N, N- disubstituted amides give aldehydes and ketones. For example,

LiR + HCON Me2 


 LiNMe2 + RCHO

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.

6.10. ORGANO ALUMINIUM COMPOUNDS


Preparation. Organoaluminium compounds may be prepared by
CH3
the following methods:
1. By the reaction of Grignard reagents with AlCl3.
RMg Cl + AlCl3 
 RAlCl2 , R2AlCl, R3 Al B
120°
one, two or three alkyl groups could combine with one Al. H3C CH3
2. By the reaction of aluminium with an organomercury Trigonal planar structure of
compound. BMe3.

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.

6LiPh + Al2 C16 


 Al2 Ph6 + 6LiCl

3. On the industrial scale Al is alkylated by means of RX giving sesquichloride R3 Al2 Cl3


Trace of I
2 
2Al + 3RCl 
AlCl or AIR
R3 Al2 C13
3 3
4. Higher trialkyls are readily prepared on an industrial scale by the alkene route in which
H2 adds to Al in the presence of performed AlR3 acting as catalyst (Ziegler catalyst) to give a dialkyl-
aluminium hydride which then readily adds to the alkene.
6 CH CH
2A1 + 3H2 + 2Al2 Et6  425 K 2  
 (6 Et2 AlH)  345
2
3Al2 Et6
K

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.

C2H5 CH2CH2.C2H5 (CH2CH2)nC2H5


C2H 4
Al C2H5 Al C2H5 Al (CH2CH2)nC2H5
nC2H4
C2H5 C2H5 (CH2CH2)nC2H5

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.

6.10.1. STRUCTURE OF ORGANOALUMINIUM COMPOUNDS


In the solid and gas phase AlMe3 is dimeric and has the methyl bridged structure. Al2 Ph6 exhibits
the similar dimeric structure. In both cases the bridging Al – C distance is 10% longer than the
terminal Al – C distance. Solutions of Al2 Me6 show only one proton nmr signal at room temperature
due to the rapid interchange of bridging and terminal Me groups. In Al2 Me6 the terminal Al – C
distances are 195 pm and the bridging distances 212 pm, the bridging Al – C – Al angle is 76°. In
general AlR3 molecules are bridged dimers in the solid state except when R is very bulky such as
tertiary butyl. The crystal structure of Al2 Ph6 shows phenyl as bridging groups and the terminal and
bridging.Al– C distances being 196 pm and 218 pm respectively.The bridging Al – C – Al angle is
measured to be 77°.

H3C C6H5

CH3 H5C 6 218 pm C6H5


H3C 212 pm 77°
78°
Al Al 270 pm Al 196 pm
261 pm Al 195 pm H5C 6
H3C C6H5
CH3
C6H5

Structure of Al2(CH 3)6. Structure of Al2(C 6H5)6


The bridges Al – CH3 – Al or Al – C6H5 – Al have three centre-two electron (3c – 2e) bonds
involving sp3 hybrid orbitals on Al and C. The four terminal Al – C bonds are normal two centre-
two electron (2c – 2e) bonds. The Al – C bridged bonds are longer than the terminal Al – C bonds.
Overlap of the orbitals is shown below.

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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

6.10.2. Applications of organoaluminium compounds


Some important reactions of organoluminium compounds are given below.
1. For the preparation of organometallic compounds. Organoaluminium compounds being
inexpensive and reactive are used to prepare other organo metallic compounds. For example,
4(CH3)3 Al + 3SnCl4 + 4NaCl 3 (CH3)4 Sn + 4NaAlCl4
Tetramethyl tin
2. In the production of high linear -alcohols
The high linear trialkyl aluminium formed as an intermediates in the production of high linear
-olefins are oxidised with air and on subsequent hydrolysis give alcohols.
3 H2O
[Al(C2 H 4 )n Et]3  O 2   Al[O(C2 H 4 ) n Et]3   Al(OH)3  3Et(C2 H 4 )n OH
2
For example, butanol is obtained by air oxidation of tributyl aluminium in toluene at 40°C
followed by hydrolysis with 10% aqueous H2SO4.
40 C, O (air)
2 2 10%H SO
4  3 BuOH
Bu 3 Al 
 (BuO)3 Al 
toluene
3. As high polymer catalysts.
Organoaluminium compounds are used as a component of the Ziegler Natta catalyst for
polymerisation of olefins and dienes. The Ziegler Natta catalysts are the main group organometallic
compounds of Al and transition metal compounds. Some common examples of such catalysts for
obtaining different products are
High density polythenes: TiCl4 – Al Et2Cl, TiCl4 – Al Et3
Polypropylenes : TiCl3 – Al Et2Cl
Butadiene rubbers : CoCl2 – Al Et2Cl
Ethylene – propylene rubbers : VOCl3 – Al2Et3Cl3
4. In Dimerization of olefins
Alkylaluminium reacts with ethylene as a single catalyst to produce molecular alkyl
compounds. However, with propene and butene, dimerization reactions occur as :

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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

6.11. ORGANOTIN COMPOUNDS


Preparation
Organotin compounds may be prepared by the following methods:
1. Reaction with organoaluminium compounds. Organotin compounds may be prepared by
reaction of tin halides with organoaluminium compounds.
4R3Al + 3 SnX4 3R4Sn + 4AlX3
The reaction forms AlX3 which easily forms the complex RnSnX4–n. The formation of this
complex lowers the yield of R4Sn. Therefore, the reaction is carried out in the presence of stronger
complexing agents for further alkylation to proceed easily in the presence of AlX3.
2. Wurtz reaction. Alkyl tin compounds may be prepared by treating tin halides with alkyl
halides in the presence of sodium. This reaction is known as Wurtz reaction.
Sn X4 + 4 RX + 8 Na R4Sn + 8 NaX
3. By Grignard reactions. The organotin compounds are prepared by Grignard reactions using
ethyl ether or ethyl ether-hydrocarbon mixture as solvent.
4 R MgX + SnX4 R4Sn + 4 MgX2
3 R4Sn + SnCl4 4R3SnCl
R4Sn + SnCl4 2R2SnCl2
R4Sn + 3SnCl4 4 R SnCl3
Compounds containing secondary or tertiary aliphatic groups and long chain alkyl phenyl or
vinyl groups give poor yield because of steric hindrance.
4. Direct reaction. Alkyltin can be prepared by direct reaction of alkyl halide and tin.
2RX + Sn R2SnX2
e.g. 2C2H5X + Sn (C2H5)2SnX2
This reactivity of alkyl halides follows the order
RI > RBr > RCl
For given halide, the reactivity follows the order
MeX > EtX > PrX

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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 + RX 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 = CRCOOMe + Me3SnH Me3SnCH2CHRCOOMe
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
CR2
R2Sn + R2 CO R2 Sn (cyclization)
O — CR2

Bonding and structure


The divalent Sn (II) and tetravalent Sn (IV) organotin compounds with coordination numbers
of 2, 3, 4, 5, 6 and 7 are known. The dimethyl tin chloride, Me2SnCl2 has a tendency to polymerize

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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

Associated structure of Me3SnF

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.

6.12. ORGANOTITANIUM COMPOUNDS


Preparation
1. Tetrakisneopentyltitanium is prepared by treating neopentyllithium with Ti Cl4 in ether
solution at room temperature.

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
78C
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°:
70C
TiCl4 + 4PhLi 
ether
 Ph4Ti

Tetraphenyl titanium decomposes with rising temperature and at room temperature it


decomposes to diphenyl-titanium and diphenyl.
room temp.
Ph4Ti  Ph2Ti + Ph – Ph

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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

Structure and Bonding


Cyclopentadienyl compounds are more stable and common. The compound Ti(C5H5)4 is
prepared from TiCl4 and NaC5H5 and the structure of the green black titanium compound is given
below. It is formulated as Ti (1 – C5H5)2 (5 – C5H5)2]

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

Structure of [Ti(5 – (C6H5)2 (CO)2] Structure of Ti(C5H5)2 dimer

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.

Vacant site CH3

Cl C2H5 C2H5 CH2 Cl Cl C2H5

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

CH3 Vacant site


CH3
H2C C Cl
Cl
CH2

Cl Ti C Cl Ti CH2

Cl CH2
Cl Cl Cl

Mechanism of Zeigler Natta catalyst


Another molecule of alkene is then bound to vacant site and the process is repeated again and
again as shown figure.
An advantage of the catalyst is that the polymer produced from asymmetric alkenes is
stereoregular. Such a stereoregular polymer is stronger and has higher melting point than non-
regular polymer.
The Zieglar Natta catalyst can be used for polymerisationof alkenes. It can be carried out under
mild conditions at room temperature in contrast to the original methods which require high
temperature and high pressure. These polymers have high melting points and are crystaline.

6.13. ORGANOMERCURY COMPOUNDS


The first organomercury compound was prepared by E. Frankland by the reaction between
methyl iodide and mercury under sunlight radiations.
A large number of organomercury compounds of the types R2Hg and monomeric R HgX have
been prepared since then. These are stable at room temperature and have low reactivity so that these
are not affected by air and water.

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

HgCl2 RLi RLi


  RHgCl 
 R2Hg

Properties of organomercury compounds


1. All of the alkyls except dimethyl mercury decompose on standing giving metallic mercury
and hydrocarbon even at room temperature. However, these are known to be sensitive to light.
2. RHgX are crystalline solids while Hg R2 are toxic liquids. Because of similar
electronegativities of Hg and C, the Hg—C bond is essentially covalent.
Mercury alkyls are volatile liquids at room temperature and have a considerable amount of
thermal stability.
3. Mercury alkyls or aryls react with halides of more electronegative elements forming new
organometallic or organo metalloid compounds.
(C6H5)2 Hg + SiCl4 C6H5HgCl + C6H5SiCl3
2(C6H5)2 Hg + SbCl3 (C6H5)3 SbCl2 + C6H5 HgCl + Hg

2(C6H5)2 Hg + SnCl4 2C6H5 HgCl + (C6H5)2 SnCl2


(C6H5) Hg + 2AsCl3 HgCl2 + 2C6H5 AsCl2

(C6H5)2 Hg + 2BCl3 HgCl2 + 2C6H5 BCl2


3(C6H5)2 Hg + AsCl3 3C6H5 HgCl + (C6H5)3 As
4. Organo mercury compounds are almost inert towards air and moisture which means that
mercury-carbon bond is not really cleaved by water or bases or dilute acids.

Structure and Bonding


R HgX and HgR2 compounds contain linear R—Hg—X or R—Hg—R units due to sp
hybridisation of mercury. In some cases, polymerization takes place to achieve this linearity. For
example, o-phenylene mercury could be written as
Hg

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

Applications of organomercury compounds


1. Organomercury compounds such as dimethyl mercury Hg(Me)2 or MeHgX are used for
treating seeds against fungal attack
2. Merthoiolate (sodium ethyl mercury thiosalicylate), metaphor (3–hydroxy mercuric–4–nitro–
o–cresol anhydride) and mercurochrome (merbromin 2, 7–dibromo–4 – hydroxy mercuric fluoresein)
are used externally as antiseptics.
3. Phenyl mercury acetate has been used against apple scab, a fungus diseases of the leaves and
fruit and also to kill crabgrass in lawns.
4. Some of the mercurials are used as the most powerful diuretics.
5. Mercury compounds are toxic to humans and animals. These can cause giddiness, lung
damage and even brain damage. These have been tested against human’s natural enemies.

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.

Methods of preparation of ferrocene


Ferrocene is prepared by the following methods:
1. By treating iron (I) chloride with Grignard
compound. Ferrocene can be prepared by treating iron (II) Model of Ferrocene
chloride with Grignard compound of cyclopentadiene.
FeCl2 + 2(C5H5) MgBr Fe (C5H5)2 + MgCl2 + MgBr2
2. By reaction of iron halide with cyclopentadiene in the presence of strong base. Ferrocene
is prepared by treating iron (II) chloride with cyclopentadiene in the presence of strong base like
diethylamine. The base helps to remove HCl produced during the reaction:
2C5H6 + FeCl3 + 2(C2H5)2 NH Fe (C5H5)2 + 2(C2H5)2 NH2Cl
3. By reaction of iron halide with sodium cyclopentadienide. Cyclopentadiene is first converted
into sodium cyclopentadienide by treating it with finely dispersed sodium in tetrahydrofuran (THF).
THF
1
C5H6 + Na   C5H5 Na + 2 H2

* Not in U.G.C syllabus

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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

3. Mannich condensation. Ferrocene reacts with formaldehyde in the presence of


dimethylamine to give mono-substituted ferrocene. This reaction is called Mannich condensation
reaction.

— CH2 — N(CH3)2
H

Fe + H — C — O + (CH3)2NH
— Fe

4. Sulphonation. Ferrocene reacts with chlorosulphuric acid or sulphuric acid in presence of


acetic anhydride to form mono-substituted and hetero-substituted derivatives.
(CH CO) O
3 2
(C5 H 5 ) 2 Fe + HOSO3 H   C5 H 5 – Fe – C5 H 4 .SO 3 H + H 2 O
5. Reaction with mercuric acetate. Ferrocene reacts with mercuric acetate (HgOAc) to give
mono and disubstituted derivatives.
The substituted derivatives of mercuric acetate react with iodide to give iodine derivatives. This
provides an indirect method for carrying out iodination of ferrocene.

— 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

(mono substituted) (Disubstituted)


The mono and dilithium derivatives find use in the synthesis of many ferrocenyl derivatives. Some
of these are given below:

— 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

Six electron pairs from two C5H5– rings

Fig. 6.1. Valence bond description for ferrocene.

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.

6.15. OLEFIN COMPLEXES


These are organometallic complexes containing unsaturated ligands such as alkenes. Zeise
characterised the pale yellow crystalline solid of composition K[ PtCl3 . (C2H4) ], which is now
known as Zeise salt. This compound was prepared by passing ethylene gas through an aqueous
solution of potassium tetrachloroplatinate (II).

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

Structure and bonding in metal olefin complexes


The structure of the anion of the Zeise salt was properly established only in 1975. The
significant features of the structure are:
CH
2
(i) The three Cl atoms and the middle point
of the ethylene double bond form a square plane Cl
CH
2
(Fig. 6.4).
(ii) The platinum atom is present in the
centre of the square and C = C double bond of Pt
the ethylene molecule is perpendicular to the
plane containing Pt and three Cl atoms.
(iii) The C 2 H4 group is significantly Cl Cl
distorted from planarity.
Fig. 6.4.
The metal atom has filled (shown shaded)
and empty (shown unshaded) orbitals. The bonding occurs in two ways:
(i) The filled molecular orbitals of the ethylene molecule are donated to the suitably direct
vacant orbitals of the metal to form alkene  metal sigma bond. This is shown in Fig. 6.5 (a).
(ii) A back bond is formed by the overlap of the filled metal hybrid orbitals with the vacant
 MO of the olefin. This leads to a -bond. The back bonding will strengthen the Pt-olefin bond
but it should weaken the C — C bond in alkene.
This type of bonding is shown in Fig. 6.5 (b).

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 dorbital of
metal to vacant  MO of ethylene.

Fig. 6.5. Stepwise bonding in metal-olefin complex.

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182 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

The complete bonding picture is shown in H H


Fig. 6.6.
We find that the metal olefin bond is + C –
essentially electroneutral because donation and – +
back bonding balance the electron density.
Initially the alkene ligand donates two electrons +

from its -bonding MO into the vacant orbital
of the metal M. Depending upon the type of
alkene-complex formed, the excess electron + –
– C +
density accumulating on M is reduced.

6.16. ALKYNE COMPLEXES H H


Fig. 6.6. Bonding in metal olefin complex.
Organometallic compounds containing
metal atom linked to alkynes are called alkyne complexes. It has been observed that alkynes form
complexes with a variety of transition metals. In alkynes, there are two  bonds at right angles to
each other and a metal atom can be bound to each. Some of the important types of metal-alkyne
complexes are considered below:
(i) The alkyne may coordinate to only one metal atom and function like alkenes. In these
molecules, alkyne molecule occupies one of the positions like that of ethylene in Zeise salt. The
carbon-carbon triple bond of the alkyne is perpendicular to the plane of coordination. These
compounds may be prepared as shown below

PtCl2 + tBuC  C But + p – CH3C6H4NH2 


 p– CH2 C6H4NH2 (Bu2 C2) PtCl2
t
u
CB
t
Cl
Bu

C

Pt

p — CH3 — C6H4 — NH2 Cl

Fig. 16.11. Structure of p-CH2 C6 H4 NH2 (Bu2 C2) Pt Cl2.


The structure of this molecule is shown in Fig. 6.7. The alkyne occupies one of the positions
of the square planar arrangement around the metal atom and the carbon-carbon triple bond of alkyne
is perpendicular to the plane of coordination. The acetylene having two perpendicular p-bonds
donates one filled p bond to the metal and the back donation from the metal occurs mainly into
the corresponding anti-bonding p orbital of acetylene.
(ii) The two -bonds of alkynes which are perpendicular to each other are bound to the metal
atom through each of their -bonds. Here, the alkynes act as 4-electron donors by using both the
-bonds and act as bridging ligands. These types of complexes are obtained by the displacement
of the bridging carbonyl groups with alkynes at higher temperatures. For example,
Benzene
Co 2 (CO)8  PhC  CPh  PhC  CPh[Co(CO)3 ]2
Reflux
( 5  C5 H 5 )2 Ni 2 (PhC  CPh)
( C5 H 5 )2 Ni 2 (CO) 2  PhC  CPh 

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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

Fig. 6.8. Metal-alkyne complexes.

6.17. HOMOGENEOUS HYDROGENATION


By homogeneous catalyst we mean a catalyst which exists in the same phase as the reacting
substances. However, catalysts miscible in the reaction medium come under the same category. Such
catalysts have the advantage that they operate at moderate temperatures and pressures. In recent
times, a number of catalysts have been developed for the hydrogenation of alkenes, alkynes and
other unsatured aromatic and heterocyclic compounds. These are
discussed as under.

1. Wilkinson’s catalyst (cis-dihydrido catalyst)


Wilkinson’s catalyst, RhCl (PPh 3)3 was the first effective
homogenous catalyst used for hydrogenation of alkenes at near
atmospheric temperatures or pressures.

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)

A second transfer via a three centre transition state


Model of Wilkinson
i.e. reductive elimination gives alkane as shown below.
catalyst
H
Ph3P H
Rh
C

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)

2. Mono hydrido complexes


Mono hydrido complexes of rhodium such as RhHCl (PPh3)3 and RhH (CO) (PPh3) and Ir
HCO (PPh3)3 having a bound hydrogen also act as hydrogenation catalysts. For steric reasons RhH
(CO) (PPh3)3 catalyses the hydrogenation of alkenes –1 i.e. terminal olefins rather than alkenes
–2. It has also recently been used in the hydroformylation of alkenes i.e. addition of H and the the
formyl group (CHO). The process is known as oxo process.

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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)

3. Hydrogenation by f-block organometallic complexes.


The lanthanide and actinides form some organometallic complexes such as (Cp2LuH)2, (Cp2
Th H2)2 (where Cp = pentamethylcyclopentadiene group, C5Me5) which are very active for
hydrogenation of alkenes and alkynes. These are about 100 times more reactive. The process
proceeds by dissociation to monomer.
The monomer then interacts with alkene undergoing insertion to form an alkyl which undergoes
hydrogenolysis. The reaction cycle is shown as under.

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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

Reaction cycle in catalytic hydrogenation of alkene


Alkenes appear to be hydrogenated in two steps with selectivity.

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.

6.19. METAL CARBONYLS


Complexes of carbon monoxide with transition metals in
low oxidation state are called metal carbonyls. The oxidation
state of the metals in such complexes is zero, low positive or
negative. It is interesting to note that although carbon
monoxide is a weak Lewis base, yet it forms a strong bond to
the metal. Carbonyl complexes can be mononuclear, binuclear
or polynuclear.

Methods of preparation of metal carbonyls


Some of the methods of preparation of metal carbonyls
are described as under:
1. Direct synthesis. The metal carbonyls can be Model of a transition
prepared by the direct reaction of carbon monoxide with the metal carbonyl

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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  25C
 Ni(CO)4
Some other metal carbonyls require high temperatures and pressures.
For example,
200C
Fe + 5CO 
 Fe(CO)5
100 atm

200C
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

250C, 350 atm


OsO4 + 9CO   Os(CO)5 + 4 CO2
3. Photolysis or thermolysis. Higher carbonyls can be synthesised by photolysis or
thermolysis of lower metal carbonyls.
hv
2Fe(CO)5  Fe 2 (CO)9 +CO
hv
3Os(CO)5  Os3 (CO)12 +3CO

Chemical properties of metal carbonyls


1. Displacement reactions. Metal carbonyls undergo displacement reactions in which one or
more CO ligands may be displaced in contact with electron donors (Lewis bases) such as pyridine,
phosphines (R3P), isocyanides (RNC), etc. One molecule of CO is replaced by one electron pair
donor. A six electron donor (like benzene) could displace three CO molecules. Some of the common
displacement reactions are:
Fe (CO)5 + Ph3 P  Fe(CO)4 PPh3 + CO

Fe (CO)5 + 2Ph3 P  Fe (CO)3 (PPh3 )2 + 2CO

Cr(CO)6 + C6H6  3CO (C6H6) Cr (CO)3


2. Formation of carbonyl anionic complexes. The metal carbonyls can be converted into
anions known as carbonylate ions by the following methods:
(a) Metal carbonyls react with bases to give carbonylate ion

Fe (CO)5 + OH–  [Fe (CO)4 ]2– + H+ + CO2

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 

6.20. BONDING IN METAL CARBONYLS


Bonding in linear metal carbonyls (M – C – O)
Carbon monoxide has a triple bond with lone pair of electrons on both C and oxygen atom as
:C O:
(i) There is a dative overlap of the filled orbital of carbon (of CO) and suitable empty orbital of the
metal forming a dative sigma bond (M  CO). This is shown in Fig. 6.9 (a)

(a) – M + + + C O; – M C O;
 – Overlap
M  C bond
– + + – – –
M + :C O: M :C O:
+ – – + + +
 – Overlap
M  C bond

Fig. 6.9. Bonding in metal carbonyls.

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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.

Evidence in support of bonding


1. The formation of back bonding from metal to CO molecule results in decrease in electron
density on metal. This is supported by the dipole moment studies. It has been observed that the
dipole moment of M—C bond is only very low, about 0.5 D.
2. The back bonding from metal to CO is expected to increase M—C bond strength with
corresponding weakening of C  O. This is due to the fact that electrons from back bonding fill
the antibonding MOs of CO. As a result, the bonding ability of CO will decrease. Therefore, as the M—
C bond becomes stronger, the C  O bond becomes weaker. Therefore, the multiple bonding
should be evidenced by the shorter M—C bond as compared to M—C single bonds and longer C—O
bonds as compared to normal C  O triple bonds. It has been observed that the bond length in CO
molecule is 1.128 Å and in metal carbonyls, it is of the order of 1.15 Å.

Vibrational spectra of metal carbonyls


Infrared spectroscopy has given valuable support to study bonding in metal carbonyls. These
studies provide information regarding bond orders of M—C and C  O bonds. The decrease in
C—O bond order or force constant is estimated by studying the CO stretching frequency in infrared
spectroscopy.
The infrared spectra is characterised by frequency of vibration, which is related to force constant
(k) as

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.

Structure of mononuclear, binuclear and polynuclear metal carbonyls


Mononuclear metal carbonyls. The mononuclear metal carbonyls have all terminal CO groups.
The shapes are those expected from their formulae. Hexacarbonyls like Cr(CO)6 have regular
octahedral structures. Tetracarbonyls like Ni(CO)4 have tetrahedral structure. The pentacarbonyls
like Fe(CO)5, Os(CO)5 have trigonal bipyramidal shape. The shapes of some mononuclear carbonyls
are given below.

CO CO CO CO
OC CO OC

Cr Fe CO Ni

OC CO OC
OC CO
CO CO
Structures of some mononuclear carbonyls

Binuclear metal carbonyls


The binuclear metal carbonyls have different types of structures. They show metal-metal
bonding and bridging CO groups in their molecules. Their structures are described below:
(i) The binuclear metal carbonyls, M2(CO)10 where M = Mn, Ti or Re have metal-metal bonding
in their structures. Each metal has octahedral arrangement of CO groups. The structure of Mn2(CO)10
is shown below.

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.

Polynuclear metal carbonyls


The structures of polynuclear metal carbonyls are more complex. They contain metal-metal
bonds and terminal and bridging carbonyl groups. The structures of some polynuclear carbonyl are
discussed below:
Among the trinuculear carbonyls known at present, crystalline Os3(CO)12 and Ru3(CO)12 have
the structures as shown below. In this structure, the metal atoms form an equilateral triangle with
no bridging CO groups. All the twelve CO groups are terminal. The structure of trinuclear carbonyls,
Fe3(CO)12, is different from that of Os3(CO)12 and Ru3(CO)12. It has two bridging CO groups as
shown below. The three Fe atoms form isosceles triangle with three Fe—Fe bonds.

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

Structure of M3 (CO)12 (M = Os or Ru) Structure of Fe3 (CO)12

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192 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

SOLVED CONCEPTUAL PROBLEMS


Example 1. What are the structural consequences of back bonding into olefin * orbitals ?
Solution. There are two main consequences of back bonding into olefin * orbital:
(i) The C = C bond length increases.
(ii) The angles around carbon are reduced from about 120° (sp2 hybridized) towards angles
typical of tetrahedral carbon (sp3 hybridized) of 109.5°.
Example 2. N2 is isoelectronic with CO, but it is a poor s donor than CO. Explain.
Solution. In N2 the highest occupied molecular orbital (HOMO) has bonding character while
in CO the HOMO is weakly antibonding. Therefore, CO is better donor than N2. This is so because
species having HOMO of antibonding type have better tendency to donate these electrons to improve
its bond order.
Example 3. Give two examples of -acid ligands similar to CO.
Solution. (i) Isocyanide (RNC) (ii) Nitric oxide (NO)
Example 4. Give one example each of 3 electron donor and 4 electron donor ligand.
Solution. 3 electron donor : -allyl
4 electron donor : 1, 3-butadiene
Example 5. Give evidence to show that the lone pair on carbon in CO ligand resides in
antibonding molecular orbital ?
Solution. When CO is ionized to form CO+ i.e. one of the lone pair of electrons residing in
HOMO is removed, the C—O stretching frequency (CO) increases from 2143 cm–1 to 2184 cm–1.
This shows that bond order has increased. Therefore, the electron pair is donated from anti-bonding
MO.
Example 6. Which transition elements show preference towards metal-metal bond
formation among metal carbonyls ?
Solution. Heavy transition elements of second and third series form stable metal-metal bonds
than first row transition metals. The large size of the heavier metals prefer formation of metal-metal
bond rather than CO bridges.
Example 7. The carbonyls of Mn and Co form metal-metal bonded dimeric species to
attain an 18 valence electrons configurations then why the 17 valence electrons complex V(CO)6
(V = 5 and 6CO = 12 making a total of 17 valence electrons) does not dimerise to attain 18
valence electron configuration ?
Solution. In order to achieve 18 valence electron configurations, V(CO)6 whould have to
dimerize having V-V bond. As a result each V would be a 7 coordinated species. This is not stable
arrangement because of stearic hindrance.
Example 8. What will happen to catalytic property if Ph3P group is replaced by Me3P in
Wilkinson catalyst ?
Solution. Complexes with alkyl phosphines are more basic and less sterically hindered than aryl
complexes. They are generally less active due to their lower tendency to dissociate. The steric bulk
in aryl complexes influences the dissociative equilibria, the orientation and complexing tendency of
the unsaturated alkene and consequently the stability of the intermediate alkyl derivative.
Example 9. Give the IUPAC names of Fe(CO)5 and [(CO)3Co(CO)2 Co(CO)3]
Solution. Fe(CO)5 : Pentacaronyl iron
[(CO)3 Co(CO)2Co(CO)3] : Di––carbonylbis(tricarbonyl cobalt)

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ORGANOMETALLIC CHEMISTRY 193

Example 10. Write the IUPAC names of the following :


(a) [Mn (CO)5(C2H4)]+
(b) [(CO)5 – Mn – Mn(CO)5]
(c) [(CO)3 Co(CO)2Co(CO)3]
(d) Fe(C5H5)2
(e) Fe2(CO)4(C5H5)2
Solution. IUPAC names of the compounds are given as follows:
(a) Pentacarbonyl (ethylene) manganese (+1)
(b) Bis (pentacarbonylmanganese)
(c) Di––carbonylbis(tricarbonylcobalt)
(d) Bis (cyclopentadienyl) iron (II)
(e) Bis (5-cyclo pentadienyl) tetracarbonyldi iron
Example 11. Which of the following do and which do not obey EAN rule ?
(i) Cr (C6H6) (CO)4
(ii) CH3 Re (CO)5
(iii) Cr(CO)6
(iv) Co2(CO)6 (RC  CR)
(v) Mo (CO)3 (–C5H5)
Solution. (i) 24(Cr) + 6(C6H6) + 8(4CO) = 38 : Does not obey EAN rule
(ii) 75(Re) + 10 (5CO) + 1(CH3) = 86 Obeys EAN rule
(iii) 24(Cr) + 12(6CO) = 36 Obeys EAN rule
(iv) 54(2Co) + 12(6CO) + 4(RC  CR) + 2(Co – Co) = 72 or 36 per Co Obeys EAN rule
(v) 42(Mo) + 6(3CO) + 5(–C5H5) = 53 Does not obey EAN rule
Example 12. Both Mn(CO)5 and V(CO)6 do not obey the EAN rule (35 electrons). Mn(CO)5
achieves EAN of 36 by forming metal-metal bond Mn2(CO)10. However V(CO)6 does not demerize
to give V2(CO)12. Explain.
Solution. V(CO)6 (EAN = 35) does not form V–V bond to give V2(CO)6 because then dimer
vanadium will acquire coordination number of 7. However, this is not stable because small sized
vanadium may face steric hindrance and may not be able to accommodate seven ligands around it.
However, each Mn in Mn2(CO)10 acquires coordination number of 6 on forming Mn2(CO)10.
Example 13. Complete the following reactions:
(i) Co2(CO)8 + PhC  CPh
(ii) Fe(CO)5 + Me3SiNC
(iii) Mo(CO)6 + NaBH4
Na / Hg
(iv) Co2(CO)8 
THF

(v) Mo(CO)6 + Pyridine


(vi) KC5H5 + FeCl2
(vii) K2PtCl4 + C2H4

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Solution. (i) Co2(CO)8 + PhC  CPh Co2(CO)6 (PhC  CPh)


 CO
(ii) Fe(CO)5 + Me3SiNC   (Me3SiNC) Fe(CO)4
(iii) 2Mo(CO)6 + NaBH4 Na2[Mo2(CO)10]
Na / Hg
(iv) Co2(CO)8   2Na+ [Co(CO)4]–
THF

– CO C5H5N
(v) Mo(CO)6 + C5H5N C5H5NMo (CO)5 (C5H5N)2 Mo(CO)4
– CO
C5H5N(– CO)

(C5H5N)3 Mo(CO)3

(vi) 2KC5H5 + FeCl2 (C5H5)2 Fe + 2KCl


(vii) K2PtCl4 + C2H4 K+ [PtCl3. C2H4]–
Example 14. How will you prepare Wilkinson catalyst ?
Solution. Wilkinson catalyst is RhCl (PPh3)3. It can be obtained by treating RhCl3.H2O with
Ph3P
III III I V
RhCl3. H2O + Ph3P RhCl (PPh3)3 + Ph3 PO

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

6. Which of the folowing is Wilkinson catalyst ?


(a) (5 C5H5)2 Ni2 (PhC  CPh) (b) RuHCl (PPh3)3
(c) RhCl (PPh3)3 (d) IrCl (PPh3)3
7. Which of the following is an example of four carbon bonded ligand ?
(a) Butadiene (b) Cyclopentadienyl
(c) Cyclooctatetraene (d) C3H5.
8. Which of the following has three bridging CO groups ?
(a) Co4(CO)12 (b) Fe3(CO)12
(c) Co2(CO)8 (d) Fe2(CO)9.
9. Which of the following mononuclear carbonyls does not obey EAN rule ?
(a) Fe(CO)5 (b) Ni(CO)4
(c) Cr(CO)6 (d) V(CO)6.
10. Which of the following does not have bridging carbonyl ?
(a) Fe3(CO)12 (b) Ru3(CO)12
(c) Fe2(CO)9 (d) Co4(CO)12.
11. The number of bridging carbonyl groups in Fe3(CO)12 is
(a) zero (b) one
(c) two (d) three.
12. Which of the folowing statements is not correct for alkyne complex PtCl2(But2C2) ?
(a) The alkyne molecule behaves as a 2 electron donor.
(b) The molecule tBu C  C But is no longer a straight line.
(c) The carbon - carbon bond is slightly longer than a triple bond.
(d) The molecule is monomer.
13. Which of the following metal carbonyl can be prepared by the direct interaction of finely
divided metal with CO ?
(a) Cr(CO)6 (b) Mn2(CO)10
(c) Fe(CO)5 (d) Co2(CO)8.
14. Fe2(CO)9 has
(a) one bridgine carbonyl (b) two bridging carbonyls
(c) three bridging carbonyls (d) none of the above

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)

Short Answer Questions


1. What are -bonded organometallic compounds ?
2. Give one example of a homogenous hydrogenation catalyst ?
3. Give one example each of a metal carbonyl which
(i) obeys EAN rule (ii) does not obey EAN rule.

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196 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

4. What are sandwiched compounds ? Give one example.


5. Give one method to prepare Fe2(CO)9.
6. How many bridging CO are present in Os3 (CO)12, Fe2(CO)9 ?
7. Define EAN rule and give one example.
8. How are Zeiglar – Natta catalysts obtained ? What is their utility ?
9. Give the formula of Wilkinson catalyst.
10. Which of the following has lowest CO group frequency ?
Terminal, doubly briged, triply bridged
11. Why metal-metal bond distance in Mn2(CO)10 is longer than that in Fe2 (CO)9 although both
are binuclear ?
12. Out of Pb (C2H5)4 and (C4H9)3 SnCl which one is a mixed organometallic compound and
why ?
13. How do you define haptacity ?

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

(ii) (C5H5)2 Fe + H2SO4 (CH CO) O


3 2 

(iii) (C5H5)2 Fe + LiC4H9
30. (a) Give two methods of preparation of transition metal carbonyls.
(b) What are metal olefin complexes ? Discuss the structure of [PtCl3(C2H4)]– ion.
31. (a) Discuss the bonding in metal-carbonyls. How does infrared spectroscopy help in
explaining bonding in metal carbonyls ?
(b) Write I.U.P.A.C. names
(i) [Mn (CO)5 (C2H4)]+ (ii) Fe2(CO)9
(iii) [K SbCl5 (C6H5)] (iv) [V (CO6)–
32. (a) Accidental discovery of ferrocene was a single major event in organometallic chemistry.
Discuss with the help of M.O. theory why is it so stable.
(b) What is -elimination in metal alkyls ? How can it be avoided ? Explain giving examples.
(c) Give the methods of preparation of Ni(CO4) and W(CO)4
(d) Complete the following reactions :

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ORGANOMETALLIC CHEMISTRY 199

(i) Co2(CO)8 + PhC  CPh


(ii) Fe(CO)5 + Me3SiNC
33. (a) What do you understand by -elimination in transition metal alkyls. How can it be
avoided ? Explain giving examples.
(b) Discuss the structures of the folowing :
(i) Ir(CO)12 (ii) Os(CO)9
(c) Write a short note on EAN rule as applied to organometallic compounds.
(d) Name the following organometalic compounds according to IUPAC system :
(i) Co2(CO)8 (ii) C6H6Cr(CO)3
34. (a) What are metal olefin complexes ? Discuss the structure of [PtCl3(C2H4)]– ion.
(b) Give the structure of Fe2(CO)9
(c) What is the meaning of 5 in the formula Fe(5 – C5H5)2 ?
35. (a) Write short notes on the following.
(i) The effective atomic number rule.
(ii) Back bonding in metal carbonyls.
36. (a) Give the structure of Fe(CO)9.
(b) Give the structure of Os3(CO)12
(c) Give the mode of bonding in metal conjugated diene complexes.
(d) Discuss the bonding in  metal olefin complexes. Give examples.
(e) Give classification of ligands on the basis of electrons involved.
37. What are metal olefin complexes ? Give one method of preparation of an important metal-
olefin complex. Discuss bonding in these complexes.
38. (a) Define an organometallic compound. Give the types of organometallic compounds.
(b) Explain the mode of bonding in complexes of metals with conjugated dienes.
(c) Define -acidity and give one example.
39. (a) Draw the structures of the following :
(i) Fe2(CO)9 (ii) Os2(CO)9 (iii) Mn2(CO)10
(b) Write IUPAC names of the following compounds :
(i) C6H6Cr(CO)3 (ii) (C5H5)2 Fe (iii) Fe2(CO)9
40. (a) What is EAN rule ? Give two examples each of organometallic compounds in which
EAN rule is
(i) obeyed (ii) not obeyed
(b) Can infrared spectroscopy distinguish between the terminal and bridging CO groups in
the metal carbonyls ? Explain.
(c) Complete the following equations giving only the major products :
(i) KC5H5 + FeCl2 ........... (ii) Mo(CO)6 + pyridine ........
41. (a) Based on the IUPAC rules, name the following organometallic compounds :
(i) Fe (3 – C5H5)2
(ii) Mn (3 – C3H5) (CO)4
(b) Identify organometallic compounds amongst the following :

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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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