ORGANOMETALLIC COMPOUNDS

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 ORGANOMETALLIC COMPOUNDS

 A compound is organometallic if it contains at

least one carbon-metal (M-C) bond.

 ‘Metallic’ – includes metalloids such as B, Si

and As, as well as true metals.

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 CLASSIFICATION

 Organometallic compounds may be

classified by the type of M-C bond which
they contain.

 Consider the Periodic Table (Types of

Organometallic Compounds)

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4
 Hence organometallic compounds can be
classified into:
 Ionic;
 Volatile covalent;
 Covalent, electron-deficient;
 Metal-like or “interstitial”.

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 Ionic Compounds
o The organometallic compounds of highly
electropositive metals e.g. alkali metal
derivatives except Li (fairly covalent).
o They are insoluble in hydrocarbon solvents
and are very reactive towards air and H2O.
o Formation of ionic compounds is favoured
when the hydrocarbon anion may be
stabilized e.g. where the negative charge
may be delocalized over several carbon
atoms in aromatic or unsaturated system.
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o The C5H5● radical readily accepts an
electron to become C5H5 anion. Six 
electrons form a delocalized, aromatic
system similar to benzene.

o Such stable anions can form salts with

cations of electropositive metals which are
ionic in character e.g. Mg2+(C5H5)2.
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 Covalent two – centre, two – electron
bonds (2c, 2e)

 Organo compounds in which the organic

residue is bound to a metal by a normal
two electron covalent bond.
 Formed by metals of lower electro-
positivity and by non-metallic elements
e.g. the Si–C bond in Me4Si.

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 Electron-deficient (multicentre bonded)
compounds, 3c, 2e
 Elements such as Li, Be, Mg, B and Al form
compounds with bridging alkyl and aryl ligands.
 The bridging is accomplished by means of M-C-
M 3c–2e bonds e.g. Al2(CH3)6 – [Al(CH3)3]2.

 Similar structures for several dimeric AlR3

molecules are formed. 9
 Occurrence of bond-type in organo-
transition metal complexes
 Apart from the capability to form M-C σ bonds,
d-block transition elements have an important
additional property than main group elements
of being able to complex with unsaturated
hydrocarbons.
 Here M-C bonds arise from covalent interaction
between the -electron system of the
unsaturated hydrocarbon and the metal
orbitals.
 This ability of transition elements to  -bond is
associated with electrons in the d-orbitals of
the metal which are of suitable energy for
covalent bonding.
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 SYNTHESIS

 Most organometallic compounds can be

synthesized using one of four M–C bond-
forming reactions:
 between a metal and an organic halide;
 Transmetallation;
 Metathesis;
 Addition.

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 Reaction of metals with haloalkanes
and haloarenes
The net reaction of an electro-positive metal and a
halogen substituted hydrocarbon

2M + RX  MR + MX
e.g. 2Li + CH3Cl  LiCH3 + LiCl

With other active metals such as Mg, Al and Zn, the

organometal halide results e.g. synthesis of Grignard
reagents:

Mg + CH3Br CH3MgBr.

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 Transmetallation

In this reaction, one metal takes the place of

another.
M + M’R  M’ + MR

Metal M is more electropositive than M’, e.g.

2Ga + 3Hg(CH3)2  3Hg + 2GaMe3

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 Metathesis
The metathesis (double replacement) of an
organometallic, MR and a binary halide (one
part is a halogen atom and the other part is an
element that is less electronegative than the
halogen), M’X:
MR + M’X  MX + M’R

e.g. Al2(CH3)6 + 2BF3  2AlF3 + 2BMe3

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 Addition of M’-H to a multiple bond
Consider an alkene addition reaction
M’-H + CH2=CH2  M’H2C–CH3
Examples:
(i) Hydroboration
H3BOR2 + R’CH=CH2 R 2O R’CH2–CH2BH2

(ii) Hydrosilation
H2PtCl6
SiH4 + CH2 = CH2 CH3CH2-SiH3
i-PrOH
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 REACTION PATTERNS
 Oxidation
 All organometallic compounds are potentially
reducing agents.
 Compounds of the more electropositive
elements ignite spontaneously on contact
with air (pyrophoric) and explode in contact
with oxidizing agents.
 Since they react so readily with O2, moisture
and CO2, they are handled in an inert
atmosphere using inert atmosphere glove
box or Schlenk line techniques.
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Inert Atmosphere Glove Box

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 Nucleophilic (carbanion) character
 The partial negative charge of an organic
group attached to an electropositive metal
results in the group being a strong
nucleophile and Lewis base referred to as its
carbanion character.
 High carbanion character leads to reaction
with very weak Bronsted acids including H2O
and alcohols.

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Mechanism
The lone pairs on the O atom of an alcohol coordinate
to the metal followed by transfer of the proton to the
alkyl group, e.g.
(C2H5)3Ga + HO(CH3)  [R3GaOH(CH3)]  R2GaOCH3 + C2H6

H R-------H

R3Ga O R’ R Ga O
R’
R
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 Lewis Acidity
 Electron deficient organonmetallics are Lewis
acids on account of the unoccupied orbitals
on the metal e.g.
B(C6H5)3 + Li(C6H5)  Li [B(C6H5)4]

 Organometallics that are bridged by organic

groups can also serve as Lewis acids and
undergo bridge cleavage e.g.
Al2(CH3)6 + 2 N(C2H5)3  2(CH3)3Al:N(C2H5)3

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 β-Hydrogen elimination

This is a reaction in which the metal atom

extracts an H atom from the next nearest
neighbour (β) atom.
M–CH2–CH3  M–H + H2C=CH2
α β
Reverse of addition of an M–H bond to an
alkene.

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Mechanism
H
MCH2CH3  M CH2
CH2

MH + CH2=CH2
i.e.

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 MAIN GROUP ORGANOMETALLIC
COMPOUNDS
Alkali metals
Organolithium compounds
These are prepared by the reaction of the
metal with an organic halide, e.g.

C2H5Cl + 2Li  C2H5Li + LiCl

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 Other preparative routes include

Metal–hydrogen exchange

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Metal–halogen exchange

Metal–metal exchange
2Li + R2Hg  2RLi + Hg
 BuLi in hexane, benzene or ethers are
commonly used for such reactions.
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 MeLi exists as a tetrahedral cluster in the
solid state and in solution.

 Thus in MeLi, the Li atoms are at the corners

of a tetrahedron with the alkyl groups
centred over the facial planes.
 Each CH3 group is symmetrically bound to
three Li atoms leading to a 4-centre, 2-
electron bond (4c, 2e). 27
 Higher homologs exist in solution as
hexamers.
 These larger aggregates can be broken by
strong Lewis bases, such as chelating amines,
notably tetramethyl ethylenediamine
(TMEDA), Me2NCH2CH2NMe2 to give stable
monomeric alkyllithium complexes.
 Reactions of lithium alkyls are generally
considered to be carbanionic in nature and
are widely employed as stereo-specific
catalysts for the polymerization of alkenes.
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OrganoNa and organoK compounds

 Essentially ionic and insoluble in

hydrocarbons.
 Exceedingly reactive, air sensitive,
vigorously hydrolysed by H2O.
 Most important are the Na compounds
from cyclopentadiene prepared by
reductive cleavage of the C–H using Na
metal or NaH.
1
C5H6 + Na Na+ [C5H5] + H2
2

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 Sodium cyclopentadienide readily undergoes
metathesis with a variety of both p-block and
d-block elements to produce both σ – or/and
 - bonded organometallic compounds. For
example,
2Na+(C5H5) + MCl2  M(C5H5)2 + 2NaCl
where M = Mg, Fe

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Alkaline earth metals

Organic compounds of Ca, Sr, and Ba are highly

ionic and reactive whereas Be and Mg
compounds have covalent character.
OrganoMg compounds
 These are useful in organic chemistry and in
the synthesis of alkyl and aryl compounds of
other elements.
 Mg compounds are of the types RMgX
(Grignard reagents) and MgR2.
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Preparation of RMgX

Mg + RX RMgX
Preparation of MgR2

HgR2 + Mg(excess)  MgR2 + Hg

 The dialkyl or diaryl is then extracted with an
organic solvent.
 Both RMgX and R2Mg are reactive being
sensitive to oxidation by air and to hydrolysis
by H2O.
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 OrganoZn and organoCd compounds

 These are synthesized by metathesis with

alkylaluminium compounds
ZnCl2 + Al2(CH3)6  Zn(CH3)2 + [(CH3)2AlCl]2
 AlkylZn compounds are pyrophoric (ignite
spontaneously on exposure to air) and readily
hydrolyzed while alkylCd compounds react
more slowly with air.

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Organomercury compounds

Readily prepared by metathesis of Hg(II)

halides with strong carbanion reagents such as
Grignard reagents
2RMgX + HgX2  HgR2 + 2MgX2

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Electron deficient compounds of the boron
group

Organoboron compounds
 Synthesized by metathesis between boron
halides and strong carbanion reagents:
BF3 + 3CH3MgBr B(CH3)3 + 3MgBrF
 The lower alkyls inflame in air, but the aryls
are stable.

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 Like other BX3 compounds alkylboranes
behave as Lewis acids giving adducts e.g.
R3B:NR’3

 When Boron halides are treated with four (4)

equivalents of an alkylating agent, an anion
[BR4] e.g. sodium tetraphenylborate
Na[B(C6H5)4] results.
i.e. BX3 + 4NaR  Na[BR4] + 3NaX

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Organoaluminium compounds

 The alkyls of aluminium are important because

of their industrial use as catalysts for the
polymerisation of ethylene and propylene.

 Also used as reducing and alkylating agents for

transition metal complexes.

 Prepared by transmetallation with dialkyl

mercury
2Al + 3R2Hg  2R3Al or [R3Al]2 + 3Hg

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 The commercial synthesis of triethylaluminium
and higher homologs is by direct interaction of Al,
H2 and alkene at elevated pressure and
temperature.
2Al + 3H2 + 6RHC=CH2 Al2(CH2CH2R)6

 All Al-alkyls are sensitive to air and moisture;

behave as Lewis acids due to coordinative
unsaturation giving adducts such as R3Al:NR3 or
anionic species like Li[Al(C2H5)4].

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 Electron precise compounds of the carbon
group
 Compounds formed by carbon with its
congeners.
Organosilicon compounds
• Tetra alkyls and tetra aryls are thermally quite
stable.
• The chemical reactivity of Si-C bonds are
greater than that of C–C bonds because:

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1. The greater polarity of the bond (Siᵟ+–Cᵟ-)
allows nucleophilic attack on Si and
electrophilic attack on C than for C–C
compounds.
2. Displacement reactions at Si are facilitated
by its ability to form five-coordinate
transition states by utilization of d-orbitals.
 Organosilicon compounds are prepared by
metathesis using Grignard or alkyl lithium
compounds.
Li4(CH3)4 + SiCl4  4LiCl + Si(CH3)4
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Alkyl and aryl silicon halides

o These halides are important because of their

hydrolytic reactions.

o Methyl derivatives are prepared by the Rochow

process by passing MeCl over heated, Cu-
activated Si;

CH3Cl + Si (Cu)  (CH3)nSiCl4-n

Hydrolysis of the Si–Cl bond

(CH3)3SiCl + H2O  (CH3)3SiOH + HCl
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Then elimination of H2O to form Si–O–Si
2[Me3SiOH]  Me3Si–O–SiMe3 + H2O
‘Siloxane’
“Hexamethyldisiloxane”
o Siloxanes undergo redistributions reactions to
form polymers, the silicones with useful
properties such as flexibility at low
temperatures, ability to repel H2O and
resistance to air oxidation. Their low toxicity
leads to their use in medical and cosmetic
implants.
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Organo-Ge, Sn & Pb compounds
 One major difference from OrganoSi is the
decrease in M–C bond strength down the Group.
In catenated compounds, similarly, Si–Si and Ge–
Ge bonds are more stable and less reactive than
Sn–Sn & Pb–Pb bonds.
 Important compounds of Pb are Me4Pb & Et4Pb
used as antiknock agents in gasoline, i.e.
Pb(CH3)4 Pb + 4CH3●
 CH3● used as radical chain terminator in engines to
reduce the tendency toward explosive
combustion.
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Electron-rich compounds of the nitrogen
group
 The simplest synthesis is the reaction:
(O)MX3 + 3RMgX  (O)MR3 + 3MgX2
 Me3P is spontaneously flammable in air, but
the higher trialkyls are oxidized more slowly.
 Tertiary phosphines, arsines and stibines are
all good -acid ligands for d-group transition
metals.
 The oxides (R3MO) form many complexes
and function as simple donors.
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Ph3P is an important ligand useful in the Wittig
reaction for alkene synthesis.
This reaction involves the formation of
alkylidenetriphenylphosphoranes from the action of
BuLi on the quarternary halide e.g.

[(C6H5)3PCH3]+Br (C6H5)3P=CH2

This intermediate reacts very rapidly with aldehydes

and ketones to give Zwitterionic compounds which
eliminate Ph3P(O) under mild conditions to give
alkenes.
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46
ORGANOMETALLIC COMPOUNDS OF THE d-
BLOCK TRANSITION ELEMENTS
Classification of Ligands
 Ligands are classified according to the number
of electrons donated by the ligand in the
formation of the metal-ligand bond.

The 18 Electron Rule

 In main group chemistry, the octet rule in
which electronic structures can be rationalized
on the basis of a valence shell requirement of 8
electrons applies.
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 Similarly, in organometallic chemistry, the electronic
structures of many compounds are based on a total
valence electron count of 18 on the central metal
atom.
 Thus, a valence shell containing 18 electrons gives
rise to stable compounds.

Electron counting and oxidation states

 Two models are routinely used to count electrons, the
neutral-ligand method (covalent method) and the
donor-pair method (ionic method).
 Both methods give identical results for electron
counting.
 The donor-pair method may be used to assign
oxidation numbers.
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Counting Electrons
Consider (5-C5H5)Fe(CO)2Cl
Note: The symbol  is known as the hapticity. The hapticity of a
ligand is defined as the number of C atoms in the ligand that are
directly bonded to the metal.

Method A: Donor Pair Method

 This method considers ligands to donate electron pairs
to the metal.
 To determine the total electron count, we must take
into account the charge on each ligand and determine
the formal oxidation state of the metal.
 Pentahapto-C5H5 is considered by this method as C5H5,
a donor of 3 electron pairs; it is a 6-electron donor.
 CO is counted as a neutral 2-electron donor. 49
 Chloride is considered Cl, a donor of two electrons.
 Therefore, (5-C5H5)Fe(CO)2Cl is formally an iron(II)
complex. Iron(II) has 6 electrons beyond its noble gas
core. Therefore, the electron count is:
Fe(II) 6 electrons
5-C5H5 6 electrons
2(CO) 4 electrons
Cl 2 electrons
Total 18 electrons

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Method B: Neutral-Ligand Method
 This method uses the number of electrons that
would be donated by ligands if they were neutral.
 For simple inorganic ligands, this usually means
that ligands are considered to donate the number
of electrons equal to their negative charge as free
ions.
 For example,
Cl is a 1-electron donor (charge on free ion = -1);
O is a 2-electron donor (charge on free ion = -2);
N is a 3-electron donor (charge on free ion = -3).
 The oxidation state of the metal does not need to
be specified to determine the total electron count
by this method.
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 For (5-C5H5)Fe(CO)2Cl, an iron atom has 8
electrons beyond its noble gas core, and 5-C5H5,
is now considered a neutral ligand (a 5-electron pi
system), in which case it would contribute 5
electrons.
 CO is a 2-electron donor, and Cl (counted as if it
were a neutral species) is a 1-electron donor.
 The electron count is:
Fe atom 8 electrons
5-C5H5 5 electrons
2(CO) 4 electrons
Cl 1 electrons
Total 18 electrons
 The results of the two methods are equivalent; both
give 18 electrons.
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 Many organometallic complexes are charged
species, and this charge must be included in
determining the total electron count.

 In the neutral-ligand method, for anions the

charge of the complex is added as a number of
electrons to the total, and for cations the
magnitude of the charge of the complex is
subtracted as a number of electrons from the
total.

 A metal–metal single bond counts as one electron

per metal, a double bond counts as two electrons
per metal, and so forth.
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 For example, in dimeric (CO)5Mn-Mn(CO)5,
the electron count per manganese atom is,
by either method:
Mn 7 electrons
5(CO) 10 electrons
Mn-Mn bond 1 electrons
Total 18 electrons

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Electron Counting Schemes for Common Ligands
Ligand Method A Method B
H 2 (H) 1
Cl, Br, I 2 (X) 1
OH, OR 2 (OH, OR) 1
CN 2 (CN) 1
CH3, CR3 (alkyl or aryl) 2 (CH3, CR3) 1
NO (bent M-N-O) 2 (NO) 1
NO (linear M-N-O) 2 (NO+) 3
CO, PR3 2 2
NH3, H2O 2 2
=CRR’ (Carbene) 2 2
H2C=CH2 (Ethylene) 2 2

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Electron Counting Schemes for Common Ligands
Ligand Method A Method B
CNR 2 2
=O, =S 4 (O2, S2) 2
η3-C3H5 (π-allyl) 4 (C3H5) 3
≡CR (Carbyne) 3 3
≡N 6 (N3) 3
Ethylenediamine (en) 4 (2 per nitrogen) 4
Bipyridine (bipy) 4 (2 per nitrogen) 4
Butadiene 4 4
η5-C5H5 (Cyclopentadienyl) 6 (C5H5) 5
η6-C6H6 (Benzene) 6 6
η7-C7H7 (Cycloheptatrienyl) 8 (C7H7) 7
η8-C8H8 (Cyclooctatetraene) 8 8
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Both methods of electron counting are
illustrated for the following complexes.
Complex Method A Method B
[Re(CO)5(PF3)]+ Re(I) 6 e- Re 7 e-

5 CO 10 e- 5 CO 10 e-
PF3 2 e- PF3 2 e-
Charge * Charge -1 e-
Total 18 e- Total 18 e-
[Ti(CO)6]2- Ti(2-) 6 e- Ti 4 e-
6 CO 12 e- 6 CO 12 e-

Charge * Charge 2 e-
Total 18 e- Total 18 e-
* Charge on ion is accounted for in assignment of oxidation state to metal 58
 The electron-counting method of choice is a
matter of individual preference.
 Method A includes the formal oxidation
state of the metal; Method B does not.

Exercise
Verify by both electron counting methods,
that [(5-C5H5)Fe(CO)2] and [Mn(CO)6]+ are
both 18-electron ions.

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Bonding in complexes
MO Theory of Octahedral Complexes
 A d-metal atom can utilize up to 9 orbitals
(one s, three p and five d) to form MOs.
 For coordination No. N, N bonding and N
antibonding orbitals can be formed, with 9-N
d-orbitals remaining unused as non bonding
orbitals.
 Thus a complex with N metal ligand bonds
has the following MO scheme:
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Metal Molecular Ligand
Orbitals Orbitals Orbitals

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 In the case of six–coordination, this scheme
corresponds to six bonding orbitals, three
non-bonding and six anti-bonding orbitals.
 Filling the N bonding and 9-N non-bonding
orbitals (but none of the anti-bonding)
requires nine electron pairs. This conclusion
suggests an 18-electron rule optimum for d-
block complexes as the analog of the Lewis
octet rule for main group elements.
 In an Oh environment, the metal orbitals
divide by symmetry into four sets.
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 Metal Orbital Symmetry Label
s a1g (non-degenerate)
px, py, pz t1u (triply degenerate)
dxy, dxz, dyz t2g (triply degenerate)
dx2-y2, dz2 eg (doubly degenerate)

 Six symmetry adapted linear combinations

(SALCs) of the 6 ligand orbitals can be formed.
63
Basis of the 18–electron rule

 The 18 electron rule arises mainly from the

kinetic stability which may be associated
with filled electron shells.
 Consider a qualitative MO diagram for an Oh
complex ML6.

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 Metal Molecular Ligand
Orbitals Orbitals -Orbitals

t1u*

a1g* Antibonding
4p (t1u) LUMO
eg*
4s (a1g) o eg
E HOMO
3d (eg + t2g) t2g Nonbonding
t1u
eg

a1g
t1u Bonding

a1g
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• In an Oh environment the eg (dx2-y2 and dz2)
orbitals of the metal form -bonding and -
anti-bonding MOs with ligand orbitals of
suitable symmetry whereas the t2g (dxy, dxz
and dyz) are non–bonding.
• The metal 4s and 4p orbitals also form -MOs
with appropriate ligand orbitals.

66
Note
 18 e’s are required to fill all the bonding and
non–bonding MOs in the complex.
 These electrons come both from the metal
and from the ligands.
 Kinetic stability of the complex will be
achieved if no low-lying orbitals are available
into which electrons may be promoted to
initiate thermal decomposition or donated as
in nucleophilic attack.
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 Stability is unlikely to be attained if bonding
or non-bonding MO’s are empty i.e. less than
18 electrons are present, hence the MO
explanation of the 18–electron rule.
 Even when 18 electrons are present a
compound will be thermally stable only
where the energy gap o is sufficiently large.

68
Exceptions to the 18–electron rule
(i) 16-electron (d8) and d3 complexes
An important class of 16-electron complexes are those
formed by d8 metal ions, e.g. Rh(I), Ir(I), Ni(II), Pd(II),
Pt(II), and Au(III). The complexes have a square planar
distribution of ligands about the metal atom.

Oh metal complexes of d3, Cr(III) and low–spin d6, Co(III)

have high kinetic stability to ligand replacement or
exchange associate with the half filled or filled t2g
environments in which the electron density is
spherically symmetrical about the metal atom, so that
there is no favourable path for attack by polar
nucleophiles. 69
(ii) Stabilization by steric effects
There is a number of thermally stable compounds which
do not obey the 18-electron rule whose stability
explanations are based on steric effects e.g. the ‘ortho
effect’ of ortho substituted aryl complexes e.g.
(R3P)2Ni(mesityl)2 – due in part to steric inhibition by
ligands.

70
 Bonding in organometallic -complexes

 The metal-olefin bond consists of two

components:
 -donations from the ligand to the metal
and
 simultaneously π-donation from the metal
to the ligand.
 Consider the interaction of ethylene with a
metal atom
 Recall bonding in C2H4 giving
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  




Figure 1. Bonding in C2H4

Note
Two carbon p–orbitals combine to form a -
bonding (filled) and a -anti-bonding (empty)
MOs.
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 The simple alkene ligands are dihapto two
electron donors because the filled -orbital
projects toward the metal and donates electrons
to suitably oriented metal orbitals (the s, pz, dz2,
dx2-y2 or hybridized metal orbitals).

Figure 2. Donation of electron–density from filled  MO of

ethylene to a vacant metal  orbital 73
 In addition, the * orbital of the ligand can accept
electron density from filled metal orbitals of the
appropriate symmetry (the px and dxz orbitals)

Figure 3. Acceptance of electron density from a filled d orbital

into the vacant * orbital of ethylene

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Hapticity
 Hapticity (η) of a ligand is the number of its
atoms that are within bonding distance to the
metal atom.
1 – monohapto;
2 – dihapto;
3 – trihapto

 Ligands with more extended -systems may

exhibit a greater number of binding modes.
Consider cyclopentaldienyl (CP)
75
 5–C5H5 (5-CP) 3–C5H5 (3-CP) 1–C5H5 (1-CP)

Decrease by two as hapticity decreases.

Consider W(CO)2(C5H5)2
Electron count W = 6
2CO = 4
2(C5H5) = 10
Total = 20

Therefore the 18–electron rule is not obeyed.

76
 However, if one of the ligands is taken to be 5
and the other 3, 18–electron rule is obeyed.

77
Cyclooctatetraene

78
Greater number of binding modes can also be
observed in benzene

79
 PREPARATIVE ROUTES OF ORGANO-
TRANSITION METAL COMPOUNDS
 From metal salt, reducing agent and ligand
 When the metal in the metal salt is in a higher
formal oxidation state than in the
organometallic compound which is being
prepared, a reducing agent is added to the
reaction mixture. For example, reductive
carbonylation:

CrCl3 + Al + 6CO AlCl3 + Cr(CO)6

80
 Reducing agents vary from active metals such
as Al and Na to alkylaluminium compounds,
H2 and CO.

 From metal and ligand

 When the metal in the starting material is
already in a formal oxidation state suitable for
the formation of the desired product, direct
ligand substitution can occur without the
necessity to include a reducing agent in the
reaction mixture. E.g. direct combination:
Fe + 5CO Fe(CO)5
81
 From metal compound and ligand
Ligand displacement
 Metal carbonyls are particularly convenient
starting materials for the preparation of -
bonded hydrocarbon complexes. E.g.
Cr(CO)6 + C6H6 Cr(η6-C6H6)(CO)3 + 3CO

Cyclopentadienyls
 When anhydrous transition metal halides react
with sodium cyclopentadienide in THF,  -
cyclopentadienyl complexes result.
82
For example,
(i) 2Na + 2C5H6 2Na[C5H5] + H2
cyclopentadiene
(ii) 2Na[C5H5] + MCl2 M(C5H5)2 + 2NaCl
(M = Fe, Co, Ni)

 From complex transition metal anions and

halides
 Complexes which contain a transition metal in
the anion may react with

(i) Alkyl halides to yield -alkyl metal derivatives.

Such anions are formed commonly by reduction of
metal carbonyls with sodium amalgam in THF: 83
 Mn2(CO)10 Na+[Mn(CO)5]

MeI

MeMn(CO)5 + NaI

(ii) Allyl halides

A -allyl derivative is first formed which may be
converted by loss of one CO into  - allyl
derivatives either by heating or UV irradiation.

84
CH2=CHCH2Cl + [Mn(CO)5] (1-CH2CH=CH2)Mn(CO)5
1-C3H5 (-allyl)
 or UV,
CO
(3-CH2CHCH2)Mn(CO)4
3-C3H5 (-allyl)

CH
CH2 CH2
Mn
OC CO
OC CO
 LIGANDS
 A large number of ligands are found in
organometallic complexes, with many
different bonding modes.
 Because the reactivity of the metal atom and
the ligands is affected by the ML bonding, it
is important to look at each ligand in some
detail.

86
 CARBONYL LIGANDS
 Metal carbonyl compounds almost always obey
the 18-electron rule, regardless of the metal’s
identity.
 The main reason for this is because the CO
ligand is both a good 𝜎-donor and a good 𝜋-
acceptor.
 The lone pair on the C-terminus of a carbonyl
can donate a pair of electrons to the metal to
form a coordinate covalent bond.
 At the same time, the 𝜋* MOs on CO can accept
electron density back from the metal as a result
of 𝜋-backbonding.
 The primary mode of CO attachment to metal atoms
is through the C-atom, :C≡O:
 Consider the molecular orbital of CO:

LUMO 2 2
6C:1s 2s 2p
2

O:1s22s22p4
8

HOMO

88
 HOMO – Occupied by an electron pair.
 Orbital has its largest lobe on carbon. CO
exerts its -donor function, donating electron
density directly toward an appropriate metal
orbital.

89
 LUMO – Two empty * orbitals. These have
large lobes on carbon than oxygen. Carbon
acts as the principal site of the -acceptor
function of the ligand.
Pi Acceptance

90
 Electrons in the d-orbital of suitable
symmetry will donate electron density into
these * orbitals of CO.
Overall interaction

91
 CARBONYL LIGANDS
 Most metal carbonyls contain metals in very low oxidation
states (and are often zero-valent).
 As shown by the IR data in Table 1, the lower the valence
of the metal, the more electropositive the metal will be
and the more electron density it will have to engage in 𝜋-
backbonding with the CO ligands.
 The stronger the M–CO 𝜋-backbonding, the lower the
energy of 𝜈(CO) will be because 𝜋-backbonding populates
the 𝜋* MO of CO.
 Notice that all of the compounds have 𝜈(CO) lower than
that for the unbound CO ligand.
 Likewise, the C≡O bond length in free CO (112.8 pm)
lengthens upon binding to the metals (typical metal
carbonyls have a C≡O bond length of ∼115 pm).
 CARBONYL LIGANDS
Table 1. Infrared data for the 𝝂(CO) stretch in a series of
octahedral metal carbonyls.

Compound (CO), cm-1

Free CO 2143
[Ti(CO)6]2 1750
[V(CO)6] 1860
[Cr(CO)6] 2000
[Mn(CO)6]+ 2090
 CARBONYL LIGANDS
The 18-electron rule is obeyed so frequently
with metal carbonyls that it can often be used to
predict the products of the reaction of a metal
with CO(g).
For example, when Ni0 (which is d10) reacts with
gaseous carbon monoxide, the organometallic
product must contain four CO ligands in order to
satisfy the 18-electron rule.
Indeed, the product of this reaction is the
tetrahedral Ni(CO)4.
 CARBONYL LIGANDS

Likewise, when Fe0 (which is d8) reacts with CO(g),

the expected product is Fe(CO)5, which has a
trigonal bipyramidal molecular geometry.
Because Mn0 (d7) has an odd number of valence
electrons, it reacts with CO to form the binary
compound Mn2(CO)10, whose structure is shown in
Figure 4.

Figure 4. Structure of Mn2(CO)10.

 CARBONYL LIGANDS
The CO ligands on each Mn(CO)5 subunit are
staggered with respect to the other half of the
molecule.
Each Mn has 7 electrons from the metal, 1
electron from the Mn–Mn bond, and 10
electrons from the five CO ligands, for a total of
18 valence electrons, in accordance with the 18-
electron rule.
The carbonyl ligand can also act as a bridge
between two metals, as is the case for Co2(CO)8
in the solid state, which has the molecular
structure shown in Figure 5.
 CARBONYL LIGANDS

Figure 5. Structure of Co2(CO)8 in the solid state.

 When the CO ligand acts as a symmetrical bridge, as it

does in Figure 5, the 𝜎sp MO on the ligand can donate
its pair of electrons to the d-orbitals on two metals
simultaneously, as shown in Figure 6(a).
Thus, in the formalism for counting electrons,
only one electron per bridging ligand can
“belong” to each metal.
 CARBONYL LIGANDS

Figure 6. (a) Sigma donation and (b) 𝜋-backbonding in

symmetrical bridging metal carbonyls.
E.g. in Co2(CO)8 each Co atom has 9 electrons
from its valence shell, 1 electron from the Co–Co
bond, 2 electrons from each of the three
terminal carbonyls, and 1 electron from each
bridging CO, for a total of 18 valence electrons.
 CARBONYL LIGANDS
The vibrational frequencies of bridging carbonyls
are considerably lower in energy than those for
terminal carbonyls.
If a carbonyl ligand were to bridge three metals,
the 𝜈(CO) stretching frequency would shift to
even lower wavenumbers.
Note that the 𝜋* MO on the carbonyl ligand is
populated by pi-backbonding from both of the
metal centers, as shown in Figure 6(b).
 NITROSYL LIGANDS
Similar to carbonyl, the nitrosyl ligand is a good
𝜎-donor and a good 𝜋-acceptor.
It can also serve as either a terminal ligand or a
bridging ligand, as shown by the examples
illustrated in Figure 7.

Figure 7. (a–d) Examples of organometallics containing

nitrosyl ligands.
 NITROSYL LIGANDS
 Two modes of bonding are possible.
 When the ligand has a +1 charge, it contains a N≡O
triple bond and is sp-hybridized. Therefore, it tends
to form a linear (165–180o) M–N≡O bond angle in
its compounds, as shown in Figure 8(a).
 Because of the triple bond, the 𝜈(NO) stretching
frequencies occur at high wavenumbers,
approximately in the range of 1610–1830 cm1.
 On the other hand, NO has an N=O double bond
and sp2-hybridization, so it will bind to the metal in
a bent configuration (119–140o), as shown in Figure
8(b).
 NITROSYL LIGANDS

Figure 8. A comparison of the two modes of bonding for nitrosyl

ligands: (a) NO+ is sp-hybridized and linear, while (b) NO is
sp2-hybridized and bent.
 NITROSYL LIGANDS
 In this bonding mode, the 𝜈(NO) stretching
frequencies are shifted to the 1520–1720 cm1
range.
 As was the case for bridging carbonyls, the 𝜈(NO)
stretching frequencies are lower in energy than
their terminal counterparts.
 E.g. the terminal 𝜈(NO) stretching frequencies occur
at 1683 and 1625 cm1 in Figure 7(c), while the
bridging 𝜈(NO) stretch occurs at 1499 cm1.
 When CO and NO are both present as ligands, as is
the case for the Ir complex in Figure 7(b), they
prefer to be cis with respect to each other so as to
minimize the competition for electron density from
the same d-orbital in their 𝜋-backbonding.
 NITROSYL LIGANDS
 The compound in Figure 7(d) has been used as a
vasodilator to lower blood pressure.
 The NO ligand is easily released in vivo, where it
activates the enzyme guanylate cyclase. This
enzyme is responsible for the catalytic conversion of
guanosine triphosphate (GTP) into 3′, 5′ -cyclic
guanosine monophosphate (cGMP), which causes
smooth muscle relaxation from the interior walls of
the arteries.
 The erectile dysfunction (ED) drug Viagra functions
by blocking the enzyme phosphodiesterase type 5
(PDE-5) inhibitors. PDE-5 is responsible for the
reuptake of cGMP thus Viagra works by increasing
blood flow to your penis, which helps you have and
keep an erection.
 PHOSPHINE LIGANDS

 Phosphines are among the most prevalent ligands in

organometallic chemistry.
 Similar to CO, PR3 ligands and their related congeners
(P(OR)3, AsR3, SbR3, and SR2) are good 𝜎-donors and
good 𝜋-acceptors.
 The sp3-hybridized orbital on the phosphine coordinates
to an empty orbital on the metal via 𝜎-donation.
 At the same time, a filled d-orbital on the metal can 𝜋-
backbond to the phosphine.
 Thus, for a series of isoelectronic metal phosphines, the
P–R bond length increases as the charge on the metal
becomes more negative (making the metal a better 𝜋-
backbonder).
 PHOSPHINE LIGANDS

 Phosphines are useful metals for probing

organometallic reactivity for several reasons.
 First, the energy of the frontier MOs can be
controlled by changing the substituents on the P
atom. When the R group is an electron donor, as is
the case for PMe3, the phosphine becomes a better
𝜎-donor but a weaker 𝜋-acceptor.
 When an electron-withdrawing group such as PF3 is
used, however, the ligand is a weaker 𝜎-donor but a
better 𝜋-acceptor.
 Thus, the electronic properties of organometallic
compounds can be tuned by a suitable choice of the
phosphine substituent groups.
 PHOSPHINE LIGANDS
The second important feature of phosphines is
the tunability of their steric bulk (the “size” of a
phosphine ligand).
Organometallic compounds containing the more
bulky phosphine ligands seldom have room to
accommodate enough ligands to satisfy the 18-
electron rule.
Furthermore, the steric bulk of ligands can
influence the types of organometallic reactions
that they undergo.
Bulkier ligands, for example, can favour
dissociative reaction mechanisms.
 DINITROGEN
Dinitrogen, N2, is strictly not an organometallic
ligand, although it is sometimes found in
organometallic compounds.
It is a much sought-after ligand, as complexes can
potentially take part in a catalytic reduction of
nitrogen to more useful species.
Dinitrogen can bind to metals in a number of
different ways.
o The majority of complexes have a terminal
monohapto link, 1-N2, in which the bonding can
be considered to be like that of the isoelectronic
CO ligand (Figure 9).
 DINITROGEN

Figure 9. A terminal monohapto link showing η1-N2

o Dinitrogen is both a weaker σ donor and a weaker

π acceptor than CO, and hence is bound less
strongly; in fact only good π-donor metal atoms
bind N2.
o Like CO, the N2 ligand has a distinctive IR stretching
band lying in the range 2150–1900 cm1.
 DINITROGEN
A dinitrogen molecule can participate in two
bonding interactions and bridge two metal atoms
(Figure 10(a)).

(a) (b)

(c)
Figure 10. (a c)
 DINITROGEN
If the backdonation to the nitrogen is extensive in
this kind of complex, it can formally be considered
to have been reduced to a hydrazine (Figure 10(b)).
Occasionally, dinitrogen ligands are found bound in
a dihapto (η2) side-on fashion (Figure 10(c)).
In these complexes the ligand is best considered
analogous to an η2-alkyne.
 ETHYLENE AND RELATED LIGANDS
 When an alkene acts as a ligand, as ethylene does in
Zeise’s salt, K[PtCl3(2-C2H4)] it binds to the metal in a
sideways manner, where the C–C 𝜋b MO donates
electron density to an empty orbital on the metal, as
shown in Figure 11, and the 𝜋* MO accepts electron
density back from a filled d-orbital on the metal.
 As a result, the C=C bond is weakened by both the 𝜋-
donation and the 𝜋-backbonding interaction.
 The C=C bond length in free ethylene is 133.7 pm; in
Zeise’s salt it increases to 137.5 pm and it is as large as
143 pm in [Pt(PPh3)2(C2H4)], where the metal is
electron-rich as a result of the low oxidation number
and donor ligands.
 ETHYLENE AND RELATED LIGANDS

Figure 11. Bonding modes in a 𝜋-ethylene organometallic.

Recall bonding in organometallic -complexes

discussed earlier.
STRUCTURAL ANALYSIS OF CARBONYL
COMPLEXES
 Structural analysis of carbonyl complexes
can employ the following techniques:
 IR spectroscopy
 NMR spectroscopy 1H and 13C
 Mass spectroscopy
 UV/Visible

114
IR SPECTROSCOPY

 IR spectroscopy is useful in two aspects:

1) Since IR bands depend on molecular
geometry, determination of such bands can
provide several alternative geometries for a
compound.

2) Position of IR band can indicate the function

of a ligand, e.g. terminal, bridging modes.

115
IR bands

 IR bands are due to change in the dipole

moment of a molecule.
 Vibrational modes are infrared active.
 Carbonyl complexes provide convenient
examples of vibrations that are visible and
invisible in the IR spectrum.

116
Monocarbonyl complexes
These have a single C–O stretching mode. Note
that free CO absorbs at 2143 cm-1.

Dicarbonyl complexes

Two geometries are possible – linear and bent.

Linear
O–C–M–C–O

117
Bent
M
C C
O O

Symmetrical stretch

O C M C O
IR-Inactive
M
C C
O O
IR-Active
118
Anti-symmetric stretch

O C M C O
IR-Active

M
C C
O O
IR-Active

119
 Hence single band for linear orientation and
two bands for non–linear orientation
observed.

Complexes containing three or more carbonyls

Predictions are not quite simple for these
complexes because of the following reasons:
 Overlapping bands such that they become
indistinguishable;
 Low intensities of bands;
 Isomers may be present.
120
 However, in carbonyl complexes the number of C–O
stretch bands cannot exceed the number of CO ligands.
 The alternative is possible i.e. more CO than IR bands
especially when there are IR–inactive vibrations.
Examples can be found in highly symmetrical complexes.

OC–M–CO
Linear.
 Complexes that show these structures show a single
carbonyl band in the infrared spectrum.
121
POSITION OF IR BANDS
Position of IR peaks is affected by:

1. Charge on the complex

For isoelectronic species such as shown below:

νCO cm-1
[V(CO)6]- 1860
[Cr(CO)6] 2000
[Mn(CO)6]+ 2090

 Increase in negative charge on complex causes a

significant reduction in the energy of the C–O band
due to additional –back bonding from the metal to
the ligand.
122
2. Bonding mode

Energy decrease in this order

Terminal CO > Bridging CO > Triply bridging CO
Free CO absorbs at 2143 cm-1
Terminal M–CO absorbs between 1850 – 2120 cm-1
Bridging CO (μ2CO) absorbs between 1700 – 1850
cm-1
CO

M M
123
Triply bridging CO (μ3CO) absorbs between
1600 – 1700 cm-1
CO

M M M

 Above values suggest an increasing

occupation of the * orbital as the CO
molecule bonds to more metal atoms.

124
3. Presence of other ligands in the complex

Consider the examples shown below:

νCO cm-1
fac–Mo(CO)3(PF3)3 2026 – 2074
fac–Mo(CO)3(PCl3)3 1989 – 2041
fac–Mo (CO)3(PPh3)3 1841 – 1937

(PF3)3, (PCl3)3, (PPh3)3

-donor ability increases

125
 Since F is highly electronegative so (PF3)3 is the
weakest donor but the strongest acceptor.

 Consequently Mo (CO)3(PPh3)3 carries the

greatest electron density; it is the most able to
donate electron density to the * orbitals of the
CO ligand. Hence C–O stretch is weakest.

Summary

The greater the electron density on the metal (and

the greater the negative charge) the greater the back
bonding to CO, and the lower the CO stretch.
126
 ORGANOMENTALLIC REACTIONS AND
CATALYSIS

 Organometallic compounds undergo a rich

variety of reactions that can sometimes be
combined into useful catalytic cycles.
 Thus, organometallic reactions of particular
importance for synthetic and catalytic
processes will be discussed.

127
 SOME COMMON REACTIONS OF
ORGANOMENTALLIC COMPLEXES
1. Reaction that occur at the metal
 Ligand substitution;
 Oxidative addition;
 Reductive elimination.
2. Reactions involving modification of ligands
 Insertion;
 Nucleophilic addition;
 Nucleophilic abstraction;
 Electrophilic reactions.
128
(i) Ligand substitution
This could be either
 Associative or
 Dissociative.
 Associative mechanism
LnML1 + L2 LnML1L2 LnML2 + L1

 This is characterized by a bimolecular rate determining

step involving the substrate and incoming ligand.

• 16-electron complexes usually undergo ligand

129
substitution.
 Consider the square planar complexes
ML4 + Y ML4Y ML3Y + L
Y
L X L X
M + Y:  M
T L T L
Square planar Square pyramid
L Y L Y

T M  M

L X T L
Trigonal bipyramid Square planar
o Associative substitution is usually found with square planar d8
metal complexes such as Ni2+, Pd2+, Pt2+ and Ir+.
130
Associative mechanism in 18-electron complexes

 The mechanism is possible if the metal complex

can delocalize a pair of electrons onto one of its
ligands.
6-C6H6 4-C6H6

131
 Co(CO)3NO + PR3 ⇌ Co(CO)2(PR3)(NO) + CO

 Dissociative mechanism
 This requires the formation of an intermediate
with reduced coordination number.
ML6 ⇌ ML5 + L
ML5 + Y  ML5Y
where L = ligand e.g. CO.

132
Consider

(i) CO dissociation
Cr(CO)6 + PPh3 
130 oC
Cr(CO)5PPh3 + CO
(ii) PR3 dissociation
cis-Mo(CO)4(PR3)2 + CO  Mo(CO)5(PR3) + PR3

133
(ii) Oxidative addition
 This involves an increase in both the formal
oxidation state and the coordination
number of the metal.
 This reaction is very important in many
catalytic processes.
 The reverse reaction is referred to as
reductive elimination.

134
 This reaction occurs in complexes with
electron counts of 16 or less.

135
 Oxidative addition is possible to 18-electron
complexes, but only with the loss of a ligand
first.

136
(iii) Reductive elimination
 This is the reverse of oxidative addition.
 Here oxidation state, coordination number and
electron count decrease- usually by two units.
 Reductive elimination is favoured in complexes
with:
 Bulky ligands;
 Metal with low electron density (high oxidation
state);
 Presence of groups [e.g. CO or P(OR)3] that can
stabilise the reduced metal.
137
Example

L = PMePh2

138
2. Reactions involving modification of
ligands
(i) Insertion: Involves the insertion of a
molecule or molecular fragment into a
metal ligand bond.
LnM–X + A–B  LnM–AB–X
1
Example

139
 This reaction is an example of alkyl migration.
 The reaction is also called CO insertion (migratory
insertion) since the incoming CO molecule seems to
have been inserted into the MnCMe bond: this name
is misleading.
 If reaction above is carried out using 13CO, none of
the incoming 13CO ends up in the acyl group or in the
position trans to the acyl group; the isolated product
is one below.

140
 Reaction above involves the intramolecular transfer
of an alkyl group to the C atom of a CO group which
is cis to the original alkyl site. The incoming CO
occupies the coordination site vacated by the alkyl
group. Scheme below summarises the process.

 Scheme above implies that the intermediate is a

coordinatively unsaturated species. 141
1:1 Insertion:
 Here both the metal and the carbon atom of
the M-C bond become bonded to the same
atom of the incoming group.
Example
O
║
(CO)5Mn–CH3 + CO → (CO)5Mn–C–CH3
1

142
 O
║
(CO)5Mn–CH3 + SO2 → (CO)5–Mn–S–CH3
1 ║
O
1:2 Insertion
Here adjacent atoms of the incoming group
become bonded to the metal-carbon atom of the
M–C bond.

143
(ii) Nucleophilic addition

 A nucleophile may attack an organometallic

complex and substitute at least one
unsaturated ligand (e.g. CO or alkene).

 Addition to CO and carbene

144
 O 

C
(i) (CO)4Fe-CO + OH  (CO)4Fe O  [(CO)4Fe-H] + CO2
H

OCH3 OCH3
(ii) (CO)5Cr = C + NH2R  (CO)5CrCN+H2R
Ph Ph

NHR
(CO)5Cr=C + CH3OH
Ph 145
(iii) Nucleophillic abstraction

 Here the ligand is attacked in such a way that

part or all of the original ligand is removed
along with the nucleophile.
 Two types of abstractions,  and ,exist.
 -Abstraction

146
-Abstraction

(iv) Electrophilic reactions

 In electron rich environments the O atom of a
CO ligand is susceptible to attack by
electrophiles.
147
For example

148
Other organometallics

Cyclopentadienyl
 Because of their great stability, the 18
electron group 8 compounds: ferrocene,
ruthenocene and osmocene maintain their
ligand- metal bonds under rather harsh
conditions, and it is possible to carry out a
variety of transformations on the
cyclopentadienyl ligands: e.g. Friedel–Crafts
substitution:

149
 O O
║ ║
CH3CCl + Fe(C5H5)2 Fe(C5H5)(C5H4CCH3)

 It is also possible to replace H on a

cyclopentadienyl, Cp ring by Li:
LiBu + Fe(C5H5)2  Fe(C5H5)(C5H4Li) + C4H10
 The lithiated product is an excellent starting
material for the synthesis of a wide variety of
ring–substituted products.
150
CATALYSIS BY ORGANOMENTALLIC
COMPOUNDS

 The presence of a catalyst dramatically

increases the rate of a reaction.
 Catalysts are classified as homogeneous if
they are soluble in the reaction medium and
heterogeneous if insoluble.

151
Homogeneous catalysts
 Homogeneous catalysts
 operate at low temperatures;
 give good selectivity;
 must be separated from product.
A typical example is Wilkinson’s catalyst,

152
Heterogeneous catalysts
 Heterogeneous catalysts
 require high temperatures;
 have low selectivity;
 lead to mixtures of products.

 Above reaction is thermodynamically

favourable but does not occur at room
temperature and pressure.
153
 In the presence of metallic Ni, Cu, Pd or Pt,
the reaction is fast.
 In some cases the metal may be coated on an
inert material such as alumina (Al2O3) or
Calcite (CaCO3).
 The reaction centre is the metal surface.

154
HYDROFORMYLATION (OXO) PROCESS
 This involves the reaction of an alkene with CO
and H2, catalysed by Co or Rh salts.
 Consider Figure 12.
R2C=CH2 + CO + H2
Alkene
HCo(CO)4, , High pressure

R2CHCH2CH
║
O
Aldehyde
155
 HCo(CO)4 is a catalyst
precursor - A
substance that
requires further
activation or reaction
to produce the active
catalyst.

156
Figure 12. Accepted mechanism for the Hydroformylation process.
Steps of the Hydroformylation cycle:
1.Dissociation of CO.
2.Coordination of olefin.
3.1:2 insertion.
4. Coordination of CO.
5.Alkyl migration (CO insertion).
6. Oxidative addition (addition of H2).
7.Reductive elimination.
 Source of HCo(CO)4 is Co2(CO)8 i.e.
H2 + Co2(CO)8  2HCo(CO)4
157
 PPh3

Figure 13. Proposed mechanism for hydroformylation using a Rh-based

catalyst. 158
 The industrial application of Hydroformylation is in
the production of butanal.
Butanal Butanol
 Butanol is an important industrial solvent used in
producing higher alcohols which are employed in
detergent and plasticisers production.
 With cobalt carbonyl catalyst high temp (140-175 oC)
and pressure (200 atm) are needed.
 Branch chain aldehydes predominate over linear
molecules which are more desirable.
 Linear detergents are biodegradable.

159
MONSANTO ACETIC ACID PROCESS

 Consider Figure 14.

 Monsanto acetic acid process involves the
reaction of CH3OH with CO and catalysed by
Rh catalyst to give CH3COOH.
 CH3OH is commercially produced by:
CO + 2H2 CH3OH
CH3OH + CO CH3COOH

160
Figure 14. Possible mechanism for the Monsanto acetic acid process.
161
Possible steps of Monsanto acetic acid process:
1.CH3OH + HI  CH3I + H2O.
2.Oxidative addition.
3.CO insertion (alkyl migration).
4.Addition of CO.
5.Reductive elimination
Note
O
║
CH3COOH is formed by hydrolysis of CH3-C-I
162
THE WACKER-SMIDT PROCESS
 Refer to Figure 15.
 The Wacker–Smidt process is used to
synthesise acetaldehyde from ethylene using
[PdCl4]2- as the catalyst.
H2C=CH2 CH3CHO

163
Figure 15. Proposed mechanism for the oxidation of ethylene to
acetaldehyde in the Wacker-Smidt process. 164
Steps of the Wacker –Smidt mechanism:
 In the first step of the mechanism, the
tetrachloropalladate ion dissociates chloride and
coordinates to the alkene.
 In the second step, water replaces chloride.
 In the third step, water acts as a nucleophile and
attacks the coordinated alkene. This step can occur
by an intramolecular or intermolecular
mechanism.
 The dissociation of a third equivalent of Cl is
followed by a 𝛽-hydride elimination reaction. 165
Steps of the Wacker –Smidt mechanism Cont:
 Following 1,2-insertion, the Pd dissociates
acetaldehyde and undergoes reductive elimination
of HCl to make Pd(0).
 The original catalyst is regenerated by oxidation
with Cu(II) in the presence of chloride ion. In
reality, CuCl2 acts as a reprocessing catalyst.
 The Cu(I) by-product is reoxidized in aqueous
solution by molecular oxygen.

166
 METATHESIS (OLEFIN)
 This involves the formal exchange of methylene (CH2)
fragments between alkenes.
a b

C a a c c
2║  C=C + C=C
C b b d d

c d
 Metathesis is a reaction catalysed either homo- or hetero-
geneously, primarily by complexes of Mo, W, Re and some
Group 4 and 5 metals.
 Reactions occur under very mild conditions (room temperature
and 1 atm).
167
ZIEGLER-NATTA CATALYSIS
 Hydrocarbon solutions of TiCl4 in the presence of
triethylaluminium polymerize ethylene at 1 atm
pressure and ambient temperature.
 The Ziegler- Natta system is heterogeneous and the
active species is a fibrous form of TiCl3 that is formed in
situ from TiCl4 and Al(C2H5)3.
 The titanium does not have a filled coordination sphere
and acts like a Lewis acid, accepting ethylene or
propylene as another ligand.
 The reaction proceeds similar to Wilkinson’s catalyst
(alkene hydrogenation - check the main catalytic cycle;
Figure 16) except that the alkyl group (instead of a H
atom) migrates to the alkene.
168
 HYDROGENATION USING WILKINSON’S CATALYST

Figure 16. Proposed mechanism for the catalytic hydrogenation of

alkenes using Wilkinson’s catalyst.
Steps for hydrogenation using Wilkinson’s catalyst:
Ligand dissociation.
Oxidative addition.
 Coordination of olefin.
1,2-insertion.
Isomerization.
Reductive elimination.
ZIEGLER-NATTA CATALYSIS

171
Steps in the Ziegler-Natta, TiCl3 catalysed
polymerization of ethylene:

I. Addition of ethylene to the vacant

coordination site of a surface Ti atom;

II. The alkyl group is transferred to the

coordinated ethylene;

III. Another ethylene is bound to the newly

created vacant coordination site and the
process of polymerization continues.
172