Organometallic Compounds

Module IV: Organometallic Compounds (8 hrs)

Definition – Classification based on the nature of metal-carbon bond – Zeise’s salt. 18-
Electron rule. Metal carbonyls –– Mononuclear and Polynuclear carbonyls of Fe, Co and Ni
(structure only) – Bonding in metal carbonyls.
Ferrocene: Preparation, properties and bonding (VBT only).
Catalysis: Zeigler Natta catalyst in the polymerization of alkene and Wilkinson catalyst in the
hydrogenation of alkene.
References
1. P. Powell, Principles of Organometallic Compounds, 2ndEdn., Chapman and Hall, London,
1988.
2. B. R. Puri, L. R. Sharma, K. C. Kalia, Principles of Inorganic Chemistry,31stEdn. Milestone
Publishers, New Delhi 2010.
3. G. L. Meissler, D. A Tarr, Inorganic Chemistry,3rd Edn., Pearson Education, 2004.
4. J. E. Huheey, E. A. Keiter, R. L. Keiter, O. [Link], Inorganic Chemistry, Pearson 2006.

Dr. Ranimol Stephen, SJC, Devagiri, Calicut 1

What are organometallic compounds?

Defined as compounds containing direct metal- carbon (M-C) bonds, where the C-
atom belongs to an organic molecule, radical or ion.

Carbon has an electronegativity of 2.5

Most metals (M) have electronegativities < 2.0

In addition to main group metals, lanthanides, actinides, and semimetals and

elements such as B, Si, As, Se, are also considered to form organometallic
compounds, Eg: organoborane compounds such as Et3B.

Egs: H3C-Li (Methyllithium), RMgX (Grignard reagent), Ni(CO)4

(Tetracarbonylnickel), K[PtCl3C2H4] (Ziese’s salt), (C5H5)2Fe (Ferrocene).

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 Various organic moiety in organometallic compounds,

➢ Alkyl
➢ Alkenes
➢ Alkynes
➢ Carbonyls
➢ Aromatic and
➢ heterocyclic

Metal carbides and metal cyanides are not considered as organometallic compounds
because the corresponding C moiety belongs to inorganic family.
But, metal carbonyls are considered as organometallic compounds, eg: Ni(CO)4
Also, compounds with non-metal carbon bonds (M= B, Si, Se, As etc) are included in the
group of organometallics.

It is difficult to make a border between organometallic chemistry and other branches.

Dr. Ranimol Stephen, SJC, Devagiri, Calicut 3

Characteristics of metal- carbon (M-C) bond

M-C bonds may be of different types and its characteristic features :

1. - bond- 2c-2e M-C bond and is mainly found in organometallics of main group
elements ( s- and p- block elements) and group 12 (Zn-family) elements.
Egs: CH3MgBr, Ga(CH3)3, Zn(C2H5)2 etc
2. -acid ligands- Involves -donation of the ligand followed by -acceptance by the
ligand. Organometallic compounds with unsaturated organic moieties experience both
 and  bonding. These compounds are stable than compounds with only M-C 
bond.
Egs: C2H4, C5H5 - etc
3. Polarity- M-C bonds are more polar compared to C-C, that alter the reactivity of
organic moieties.

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4. Multicentre bonds- Some organometallic compounds form multicentre bonding. This is
found in alkyl compounds of Li, Be and Al.
Eg: In the tetramer of LiCH3, Li4(CH3)4, methyl bridging involves 4c-2e
bonding.
5. Ionic bond- Highly electropositive metal ions can form the ionic bonds with
carbanions stabilized by delocalisation.
Eg: Na+Ph3C-, Ca2+(C5H5-)2 etc.

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History of organometallic chemistry ( Some Important Milestones)

1827
Ziese’s salt, W. C. Ziese, Danish
Pharmacist. First transition metal
organometallic compound

1848 Edward Frankland made diethyl

zinc. Frankland coined the term
‘organometallic’
1888 Ludwig Mond, the founder of the
British chemical company ICI made
Ni(CO)4, the first binary metal
carbonyl, it is used in the refining of
Ni.
1891 Fe(CO)5 Mond Identified
1900 Grignard reagent (RMgX) Organomagnesium halides (RMgX)
synthesised by Grignard. He was
awarded the Nobel Prize in 1912
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1948 Vitamin B12 and It possesses Co-C linkage.
the B12- coenzymes Dorothy Hodgkin was awarded the Nobel Prize in
Chemistry in 1964 for the discovery of three dimension
structure of vitamin B12 by x-ray crystallography.
Vitamin B12 was synthesized by Woodward in 1973.
1951- Ferrocene Two groups independently prepared ferrocene and
52 suggested a sigma bonded structure. The sandwich
structure was proposed by Wilkinson, Fischer and
woodward.

Discovery of ferrocene initiated the fresh interest in the

field of organometallic chemistry. Within a few months of
discovery of ferrocene Fischer prepared [Cr(C6H6)2] and
shared Nobel Prize in 1973 with Wilkinson.
1955 Ziegler –Natta [Link] and [Link] and awarded Nobel Prize in 1963
catalyst
1973 First metal carbyne E.O. Fischer
complex

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Classification of organometallic compounds

Organometallic compounds can be classified in different ways. Broadly it is classified

into three.

Classification based on,

1. nature of M-C bond
2. nature of ligand and
3. nature of the metal atom involved.

Dr. Ranimol Stephen, SJC, Devagiri, Calicut 8

Classification of organometallic compounds

Organometallic compounds

Classification based on

Nature of
Nature of M-C Nature of metal atom involved
ligand

Ionic Simple OM OM of main group elements

M-C  Mixed OM OM of transition metals

 Bonded
OM of f-block elements
ligands

 and

Multicentre
bonds

M-C multiple bonds

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1. Classification based on M-C bond

(i) Ionic organometallic compounds

(ii) M-C  bonded compounds
(iii) Organometallic compounds with -bonded ligands
(iv) Organometallic compounds with  and  bonds
(v) Organometallic compounds with multicentre bond
(vi) Organometallic compounds with M-C multiple bonds

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(i) Ionic organometallic compounds

Formed by highly electropositive metals which bind the organic radical anions
electrostatically.
Compounds with maximum ionic character are those with large cations and small
carbanions.

Egs: Methyl derivatives of alkali metals- Cs+CH3-, Na+CH3-

Hydrocarbons containing sp hybridised carbon atoms give carbanions and form stable
organometallic compounds with alkalimetals.

Eg: monosodium acetylide, Na + C -  CH

R - C  CH hydrocarbons are sufficiently acidic and can easily release acetylenic

hydrogen to form acetylenic anions .

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 Carbanions with extended conjugated system can form more stable ionic compounds.

Eg: Allyl anion H 2 C = CH - CH 2  - CH 2 - CH = CH 2  H 2 C − CH − − CH 2

-

Compounds containing radical anions with delocalized - systems are more stable.

Eg: Cyclopentadienyl derivative of sodium, C5H5-Na+ ; Na+Ph3C-

Stability of the compound due to the delocalisation of the charge over the ring, C5H5-
attains the aromaticity (4n+2 rule, 6 electrons) to earn the stability.

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(ii) Compounds containing M-C  bonds

In these compounds 2c-2e M-C bonds are formed.

Metallic elements of group 2, 12, 13, 14 and 15 elements form organometallic
compounds with M-C  bond.

Es: Dialkyl compounds of Be and Mg, R2Be, R2Mg

RMgX
Pb(C2H5)4
Pb(CH3)4
Zn(CH3)2
Sn(C2H5)4

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(iii) Organometallic compounds with - bonded ligands

- electron clouds of unsaturated organic molecular species participate in bonding with

metal centre.
Egs: alkene, alkyne, butadiene cyclobutadiene, cyclopentadienyl anion, benzene, alkyl
anion, cyclooctatetraene etc.
All the available - electrons or a portion of the unsaturated skelton may participate in
bonding.
Transition metal atoms are generally form - bonded compounds.
The most important compound of this category is ferrocene

The -electrons of Metal-ethene

cyclopentadienyll anion overlap bond is a -bond
the vacant d- orbitals of metal in Ziese’s salt
and form - bonds.

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(iv) Organometallic compounds with  and  bonds

In this OM compounds, there is ligand – to- metal (L M) - bonds and metal – to-
ligand (M L) - back bonding.
This - bonding and - bonding act in a synergistic fashion to stabilize the metal- carbon
bond.

When the ligand (eg: CO ) can act as - acid ligand, OM compounds exhibit  and 
bonds.

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(v) Organometallic compounds with multicentre bond
(Nonclassically bonded organometallics)

❖ In some OM compounds the alkyl groups may act as bridging groups between metal
centres.
❖ Electron deficient multicentered M-C bonds are formed instead of 2c-2e M-C bond.

Egs: Li4(CH3)4 (4c-2e bond); Be(Me)2- polymeric form (3c-2e bond); (AlR3)2- dimeric form
(3c-2e bond).

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❖ Elements with highest tendency to form multicentre OM compounds are Li, Be, Mg, B
and Al.
❖ In these OM compounds, bonding cannot be explained by the classical concepts of
chemical bonding (2c-2e bonds), so these are called non-classically bonded OM
compounds.
(vi) Organometallic compounds with M-C multiple bonds

Carbene and carbyne forms multiple bonds with metal.

Carbene Carbyne

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2. Nature of ligand

(i) Simple organometallic compounds

OM compounds containing only,

- hydrocarbon groups or
- hydrocarbon groups + H atoms
attached to the metal

Egs: (C2H5)4Pb; (CH3)3SnH

(ii) Mixed organometallic compounds

OM compounds containing at least one hydrocarbon group along with groups other
than H atom.

Egs: R-Mg-X, (C4H9)2SnCl2

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3. Nature of metal atom

(i) OM compounds of main group elements

❖ OM compounds formed by main group elements

❖ Most of these form -covalent bond between metal and carbon
❖ OM compounds with alkali metals are ionic compounds.

(ii) OM compounds of transition metals

- Formed by transition elements

- With - bonding ligands

(iii) OM compounds of inner transition metals

- Formed by lanthanides and actinides

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3. Nature of metal atom
(i) OM compounds of main group elements
❖ OM compounds formed by main group elements
❖ Most of these form -covalent bond between metal and carbon
❖ OM compounds with alkali metals are ionic compounds.
(ii) OM compounds of transition metals
❖ Formed by transition elements
❖ With - bonding ligands
❖ In 1827, Zeise prepared Zieise’s salt, K+[PtCl3(C2H4)]-.
❖ Then d-block metal derivatives of carbon monoxide, Ni(CO)4 in 1890.
❖ Ferrocene by Kealy and Pauson in 1951.
❖ The most important ligands for d-block metals in organometallic compounds are
CO and aromatic polyenes.
❖ Transition metal can form OM compounds with alkenes, alkynes, alkyl cyanides,
alkyl isocyanides, NO etc.
(iii) OM compounds of inner transition metals
- Formed by lanthanides and actinides
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Based on the groups attached to the metal, organometallic compounds are classified into
two:
Homoleptic OM compounds and
Heteroleptic OM compounds

Homoleptic OM compounds

- Are those in which the same groups are attached to the metal.
Eg: CH3 – Zn – CH3

Heteroleptic OM compounds

- Are those in which different groups are attached to the metal.

Eg: CH3 – Zn – C2H5

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Dr. Ranimol Stephen, SJC, Devagiri, Calicut
Organometallic compounds containing  and  bonds

❑ OM compounds with both  and  interaction are more stable.

❑  - interaction occur in aryls of transition metals between the filled p  orbital of the
ligand and vacant d  orbital of the metal of the same symmetry, or between the filled d
 orbital of the metal and empty p  orbital of the ligand of the same symmetry.
d -p 
d -p 
M L M L
 

❑ This kind of multiple bonding enhances the strength of the bond and thereby the
stability of the compound.
❑ - interaction between the metal and ligand is possible in the alkynyl and alkenyl
compounds of transition metals of the type M-CCR and M-CH=CR2.
❑ Ligands act as - acceptors.
❑ CO ligands in metal carbonyls are also - acceptor ligands.

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Hapticity of ligands and nomenclature of OM
Hapticity of ligands- is the number of carbon atoms through which an organic ligand is
attached to the metal atom
Hapto comes the Greek word for fasten
It is represented by n ( where n is the number of carbon atoms of the ligand attached to
metal)
Egs: 3- allyl , 4- butadiene, 4- cyclobutadiene, 5- cyclopentadienyl etc

No. of C of ligands Representation Name

attached
1 1 Monohapto
2 2 Dihapto
3 3 Trihapto
4 4 Tetrahapto
5 5 Pentahapto
6 6 Hexahapto
7 7 Heptahapto, so on
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Ligands Examples

Monohapto CH3 in CH3-Mg-X

Dihapto H2C=CH2 in Zeise’s salt

Trihapto 3- allyl

Tetrahapto 4- butadiene

Pentahapto 5- C5H5- or 5- cyclopentadienyl or 5- Cp

Hexahapto 6- C6H6

Heptahapto 7- C7H7+ or 7- tropylium

Octahapto 8- cyclooctatetraene

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Name and formula

Bridging ligands are common in organometallic chemistry, it is designated by ,

followed by a subscript indicating the number of metal atoms bridged.

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Ziese’s salt

✓ Ziese’s salt, K[PtCl3(2-C2H4)] was prepared by Ziese in 1827.

✓ It was the first organometallic compound to be reported.
✓ In the formation of Ziese’s salt and such kind of complexes C=C - bond acts as a source
of electron pairs.
✓ Prepared by bubbling ethene through an aqueous solution of tetrachloroplatinate(II) ion
in the presence of Sn(II). Sn(II) to remove the chloride ions from Pt(II) coordination
sphere.

➢  bond is formed by the donation of electrons from filled

ethylene  orbital into an empty dsp2 hybrid orbital of Pt.
➢ - bond is formed by the back- donation of electron density
from a filled metal orbital to the * orbital of ethylene.
➢ Ethylene molecule is perpendicular to the PtCl3 plane.
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❖ In alkenes, the C=C consists of a -bond formed by the head-on overlap of the sp2
orbitals of the two carbons and a = bond formed by the sideways interaction of a 2p
orbital of one carbon and 2p orbital of the other carbon.
❖ The - interaction between the two carbons produces two MOs- a filled  bonding MO
and a vacant * antibonding MO.
❖ During complex formation with transition metal, alkene donates electron density from
the filled  BMO to the metal to form - bond.
❖ At the same time, electron density is donated back from a filled metal orbital to the
vacant  * orbital of the ligand to form  bond.
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The 18- electron rule

Rule states that thermodynamically stable transition metal organometallic compounds are
formed when the sum of the metal d electrons and the electrons supplied by the
surrounding ligands equals 18.
The conditions favouring 18 electron rule are , an electron rich metal and the ligands that
are good - acceptors.

➢ Ligands are considered as Lewis bases and can donate electrons to the metal ion
➢ Metal ion act as Lewis acid.
➢ EAN- The sum of the electrons on the metal and the electrons donated by the ligands
are called effective atomic number (EAN).
➢ Most of the stable complexes have an EAN of the next inert gas, 36 (Kr), 54 (Xe) or 86
(Rn).

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According to Sidgwick, during the formation of complexes, metal atom accept electron
pairs from the ligands until it attains an EAN of the next inert gas. This is known as EAN
rule.

✓ If a complex obeys EAN, the metal should have an outer electronic configuration of
ns2(n-1)d10np6.
✓ 18 electrons in the valence orbitals.

In a stable complex total number of electrons, ie, sum of the electrons received from
ligands and the number of electrons originally present in (n-1)d, ns and np orbitals of
metal should be equal to 18. This is known as 18 electron rule.

18 electron rule has the following advantages,

- same for all rows of the periodic table
- number is easy to recall because it is the total capacity of nine orbitals (one s,
three p and five d orbitals)
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 3 4 5 6 7 8 9 10 11 12

Total number of electrons in the (n-1)d, ns and np orbitals of free metal atom
Steps:
(i) Count the total number of electrons in the valence shell orbitals of the metal.
(ii) Add or subtract electrons depending on the oxidation state of the metal in the complex.
(iii) Count the electrons donated by the ligands to metal. In the case of CO, terminal CO
donates 2 electrons and bridging CO contributes one electron.
(iv) Count the number of electrons donated by other ligands if it is present in the complex.
(v) Count the number of electrons contributed by the metal in metal- metal bonds.
(vi) Add the electrons from all steps to get effective number of electrons.
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Egs:

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18 electron rule helps to predict the structure of complex, if we assume that the 18-
electron rule is strictly obeyed.

Eg:

Assuming that 18 e rule is obeyed, the remaining 3 electrons can only be the contribution
of the bond between two Re atoms.
The compound is expected to have triple bond between the metal atoms, ReRe.

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Metal carbonyls

➢ CO is a neutral unsaturated ligand, which can form bonds with metals.

➢ Compounds of transition metals with CO ligand are called metal carbonyls.
➢ [Ni(CO)4] was the first synthesised metal carbonyl. It was synthesised by Ludwig Mond
in 1889.
➢ The general formula of a homoleptic carbonyl is represented as Mx(CO)y.
➢ Metal carbonyls can be neutral,
Formula Oxidation state of metal
anionic or cationic.
[Mo(CO)6] 0
➢ Heteroleptic carbonyls also.
[Rh(CO)12] 0
Eg: H2[Fe(CO)4]
[Ti(CO)6]2- -2

[Co(CO)4]- -1

[Re(CO)6]+ +1

[Fe(CO)6]2+ +2 33
Dr. Ranimol Stephen, SJC, Devagiri, Calicut
Classification of metal carbonyls

Depending on the number of metal atoms present, carbonyls can be classified into two:
-Monomuclear and
- Polynuclear

Mononuclear carbonyls

Carbonyls which contain only one metal atom per molecule are called mononuclear
carbonyls.
Egs: Ni(CO)4, Fe(CO)5, V(CO)6, Cr(CO)6 etc.

Fe(CO)5 Ni(CO)4
dsp3 hybridised Fe sp3 hybridised Ni
Trigonal bipyramid Tetrahedral
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Polynuclear carbonyls

✓ Carbonyls which contain more than one metal atom per molecule are called polynuclear
carbonyls.
✓ If the metal atom present in the molecule are same, such polynuclear carbonyls are
called homonuclear carbonyls.
Egs: Fe2(CO)9, Fe3(CO)12, Co2(CO)8, Rh6(CO)16 etc
✓ If different atoms are present in the molecule, such polynuclear carbonyls are called
heteronuclear carbonyls.
Egs: Mn2Fe(CO)14, MnCo(CO)9, Co2(CO)8, MnRe(CO)10 etc
✓ Polynuclear carbonyls are further classified into two: (i) non-bridged carbonyls and (ii)
bridged carbonyls.
✓ Non-bridged carbonyls are those which contain only terminal carbonyl groups.
Eg: Co2(CO)8 in solution
✓ Bridged carbonyls are those which contain bridging carbonyl groups.
Eg: Fe2(CO)9 and Co2(CO)8 in solid state.
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➢ Dicobalt octacarbonyl exist in two forms.
➢ In the solid state , Co2(CO)8 has a bridged structure with two bridging CO groups.
➢ A non- bridged structure predominates in a solution above ambient temperature.
➢ In the bridged structure, the Co atoms are in d2sp3 hybridised state.

➢ Each of the iron atoms in diiron nonacarbonyl has three

terminal carbonyl groups.
➢ The remaining three carbon monoxide ligands act as 3-CO
groups.
➢ There is a weak Fe- Fe bond (2.46 Å) formed by sharing of
two unpaired electrons present in the 3d orbitals of iron
d2sp3 hybridised iron atom.
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Dr. Ranimol Stephen, SJC, Devagiri, Calicut
Most of the metal carbonyls obey 18 electron rule.

Complex Metal Ligand M-M bond Effective no.

electrons electrons electrons of electrons
Ni(CO)4 10(4s23d8) 4x2 =8 0 18
Cr(CO)6 6(4s13d5) 6x2=12 0 18
(7- 5(4s23d3) 7+(3x2)=13 0 18
C7H7)V(CO)3
Mn2(CO)10 7(4s23d5) 5x2=10 1 18

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Dr. Ranimol Stephen, SJC, Devagiri, Calicut
Molecular orbital theory and 18-electron rule

For an octahedral complex the most stable arrangement is ,

- bonding and non-bonding molecular orbitals (a1g, t1u, eg and
t2g) are fully occupied
- all the antibonding orbitals are empty.

➢ 18- electrons are required to fill all the nine

bonding and non-bonding orbitals.
➢ If o value is large, t2g to eg* transition is
difficult
➢ Complexes of 2nd and 3rd row transition
metals have large o values.
➢ Ligands such as CO and NO can form - back
bonding with metal.
MO diagram for an Oh complex
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Bonding in metal carbonyls

Lewis structure of CO

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Preparation of metal carbonyls of iron and nickel

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Dr. Ranimol Stephen, SJC, Devagiri, Calicut 45
Ferrocene

(5-C5H5)2Fe – [bis(cyclopentadienyl)iron

✓ Metal, Fe is ‘sandwiched’ between two cyclopentadienyl rings.

✓ These type of organometallic compounds are called metallocenes.
✓ Ferrocene and its derivatives are used as fuel additives due to its antiknock properties.
✓ Also used as catalysts in organic synthesis, as anticancer drugs and for the production of
carbon nanotubes.

Structure of ferrocene

✓ In gas phase, the preferred form is eclipsed an in

condensed phase, staggered form.
✓ The barrier to rotation is very low (~5 kJ/mol.

D5h D 5d 46
Dr. Ranimol Stephen, SJC, Devagiri, Calicut
Synthesis of ferrocene

(1) It is prepared by the reaction of ferrous chloride with the Grignard reagent
cyclopentadienyl magnesium halide, C5H5MgX.
2C5H5MgCl + FeCl2 (C5H5)2Fe + 2MgCl2
(2) Reaction of metal cyclopentadienides with ferrous halide in tetrahydrofuran.

(3) Reaction of cyclopentadiene on anhydrous ferrous halide in the presence of an

amine. The ammine facilitates the removal of the acidic hydrogen of cyclopentadiene.

(4) By the reaction of iron or ferrous oxide with cyclopentadiene at high temperature.

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Dr. Ranimol Stephen, SJC, Devagiri, Calicut
Physical and chemical properties

Orange coloured solid with mp 174oC.

❑ Stable in air, thermally stable upto 500oC.

❑ Stable towards hydrolysis.
❑ Stable towards catalytic hydrogenation of the cyclopentadienyl (Cp) ring because the pi
electron density of the ring is donated to the metal.
❑ Aromatic character.
❑ C5H5- ring behave as aromatic system.
❑ It undergoes electrophilic substitution reactions.

(1) Friedel- Crafts reactions- Acylation and alkylation

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(2) Sulphonation- with conc. Sulphuric acid in the presence of acetic anhydride ferrocene
yields ferrocene sulphonic acid.

(3) Nitration – Direct nitration of ferrocene leads to decomposition. Lithiated ferrocene is

nitrated to get nitroferrocene. It on reduction with Fe/HCl or Pd/HCl gives aminoferrocene.

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(4) Carboxylation

(5) Bromination

(6) Mannich condensation

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Bonding in ferrocene

- Can be explained on the basis of (i) VBT and (ii) MOT

(i) VBT

❑ Proposed by Fischer and Fritz.

❑ C5H5- is a strong ligand, when it approaches
Fe2+, electron pairing in the 3d level takes
place.
❑ Two 3d, one 4s and three 4p orbitals of
Fe2+ hybridise to form d2sp3 hybridised
orbitals.
❑ Each C5H5- ion donates 3 electron pairs.c

❑ Six empty d2sp3 hybrid orbitals of Fe2+ accommodate the six electron pairs form Cp.
❑ No unpaired electron. Diamagnetic in nature.
❑ 18 electron. So it is stable.
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Dr. Ranimol Stephen, SJC, Devagiri, Calicut
(ii) MOT of the structure of ferrocene

➢ In planar pentagonal C5H5 ring, all C are sp2 hybridised.

➢ Linear combination of five p orbitals yield five MOs.
➢ MOs of two C5H5 rings combine to yield 10 MOs.
➢ These 10 MOs, ligand group orbitals combine with nine valence
orbitals , five 3d, one 4s and three 4p orbitals to form 19 MOs.
➢ Nine Bonding and non- bonding MOs, 10 are ABMOs.
➢ 18 electrons are arranged in 9 bonding and non-bonding MOs.
➢ 10 ABMOs are vacant.
➢ No unpaired electron.
➢ Diamagnetic in nature.

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Dr. Ranimol Stephen, SJC, Devagiri, Calicut
Applications of organometallic compounds

1. As catalyst

✓ OM compounds finds application as catalyst in hydrogenation of alkenes,

hydroformylation reactions, oxidation of alkenes, stereoselective polymerization of
alkene.
Ziegler Natta Catalyst for the syntesis of stereoregular polymers.
Free radical
polymerisation resulting
in branched PE (LDPE).

Ziegler- Natta
polymerisation
resulting in linear PE
(HDPE)
Ziegler- Natta catalyst consists of TiCl3 or TiCl4 , along with co-catalyst aluminiumtrialkyl
Al(C2H5)3 or the dimer Al2(C2H5)6.
Role of aluminiumalkyl is to activate TiCl4 catalyst and sterically control the active sites.53
Dr. Ranimol Stephen, SJC, Devagiri, Calicut
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Dr. Ranimol Stephen, SJC, Devagiri, Calicut
Wilkinson’s catalyst- for hydrogenation of alkenes

Wilkinson’s catalyst is (PPh3)3RhCl- tris(triphenylphosphine)rhodium(I)chloride

▪ It is prepared by treating alcoholic triphenylphosphine with RhCl3.

▪ It is a homogeneous catalyst used for the selective hydrogenation of terminal double

bonds leaving other double bonds unhydrogenated due to steric reasons.
▪ The hydrogens are preferentially transferred to cis positions.
▪ Reaction takes place at room temperature and under 1 atmospheric pressure.

▪ One drawback is the regenerated catalyst remain in the solution and is difficult to
remove.

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Dr. Ranimol Stephen, SJC, Devagiri, Calicut
2. As synthetic reagents

Several OM compounds are important reagents in organic synthesis.

Grignard reagent is an example.

Dr. Ranimol Stephen, SJC, Devagiri, Calicut 56

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Dr. Ranimol Stephen, SJC, Devagiri, Calicut
Problems

58
Dr. Ranimol Stephen, SJC, Devagiri, Calicut