AJELIAS L7-S1

Unique reactions in organometallic chemistry

Oxidative Addition
Reductive Elimination
Migratory Insertion
- Hydrogen Elimination
 AJELIAS L7-S2

Oxidative addition

When addition of ligands is accompanied by oxidation of

the metal, it is called an oxidative addition reaction
LnM + XY Ln(X)(Y)M
dn dn-2
OX state of metal increases by 2 units H2 oxidative
H
Ph3P PPh3 addition H PPh3
Rh Rh
Coordination number increases by 2 units Ph3P Cl Ph3P Cl
PPh3
2 new anionic ligands are added to the metal Rh+1 Rh+3

Requirements for oxidative addition

availability of nonbonded electron density on the metal,

two vacant coordination sites on the reacting complex (LnM), that is,
the complex must be coordinatively unsaturated,

a metal with stable oxidation states separated by two units; the higher
oxidation state must be energetically accessible and stable.
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Examples of Oxidative addition : Cis or trans ?

Cl
Cl PPh3
Ir 18E
Cl2 Ph3P CO
Cl
O
Cl PPh3 O2 O PPh3
Ir Ir
Ph3P CO Ph3P CO
16E Cl

Me Me
MeI
Cl PPh3 I PPh3
Ir Ir
Ph3P CO Ph3P CO
I Cl

Homonuclear systems (H2, Cl2, O2, C2H2) Cis

Heteronuclear systems (MeI) Cis or trans
 AJELIAS L7-S4
An important step in many homogeneous catalytic cycles

Hydrogenation of alkenes- Wilkinson catalyst

H
H2 oxidative
Ph3P PPh3 addition H PPh3
Rh Rh
Ph3P Cl

Often the first step of the mechanism

Ph3P Cl
PPh3
Rh+1 Rh+3
Methanol to acetic acid conversion- Cativa process
CH3
I CO CH3I I CO
Ir Ir
I CO I CO
Ir+1 Ir+3 I
Pd catalyzed Cross coupling of Ar-B(OH)2 and Ar-X Suzuki Coupling

Br
Br
Ph3P Pd PPh3 Pd
Ph3P PPh3
Pd0 Pd+2
The more electron rich the metal, more easy is the oxidative addition
 AJELIAS L7-S5

Oxidative addition involving C-H bonds and cyclo/ortho metallation

Agostic interaction

This type of reactions help to activate unreactive hydrocarbons such

as methane known as C-H activation
 AJELIAS L7-S6

Reductive elimination

Almost the exact reverse of Oxidative Addition

CH3 Ph2
Ph2
P CH3 P CH3
reductive elimination + H3C CH3
Pt Pt
165 C, days P CH3
P CH3
Ph2 Ph2
CH3
Pt4+ Pt2+

Oxidation state of metal decreases by 2 units

Coordination number decreases by 2 units
2 cis oriented anionic ligands form a stable bond and leave the metal

Factors which facilitate reductive elimination

a high formal positive charge on the metal,
the presence of bulky groups on the metal, and
an electronically stable organic product.
Cis orientation of the groups taking part in reductive elimination is a
MUST
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Final step in many catalytic cycles

Hydroformylation ( conversion of an alkene to an aldehyde)

Sonogashira Coupling (coupling of a terminal alkyne to an aryl group

Cativa Process (Methanol to Acetic acid)

 AJELIAS L7-S8

Migratory Insertion

X L
+L
M Y [M-Y-X] M Y X
dn dn
No change in the formal oxidation state of the metal
A vacant coordination site is generated during a migratory insertion (which
gets occupied by the incoming ligand)

The groups undergoing migratory insertion must be cis to one another

CH3 Ph3P O
OC OC
CO C
Mn + PPh3 Mn CH3
OC CO OC CO
OC OC

These reactions are enthalpy driven and although the reaction is

entropy prohibited the large enthalpy term dominates
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Types of Migratory Insertion

X X

M A B M A 1, 1 - migratory insertion

B
X
X
A B 1, 2 - migratory insertion
M
M A
B

CO O
CH2CH2R 1, 1-migratory Ph P CCH2CH2R
Ph3P insertion 3
Rh Rh
OC PPh3 OC PPh3

H
R 1, 2-migratory CH2CH2R
Ph3P
Ph3P insertion
Rh Rh
Ph3P OC PPh3
CO
 AJELIAS L7-S11

Stability of Bonded alkyl groups as ligands

Joseph Chatt 1962 - 68

Br PEt3 H3CH2C PEt3 H PEt3 CH2

EtMgBr Heat +
Pt Pt Pt
Et3P Br Et3P Br Et3P Br
Pressure CH2
poor yields
unstable

Ph3P
n - BuLi Pt
cis PtCl2(PPh3)2
Ph3P

Ph3P + Ph3P
Pt + Pt
60 C, Ph3P
Ph3P
sealed tube

Ph3P CH3
Pt No decomposition
Ph3P CH3 60 C
sealed tube

Why does some bonded alkyl complexes decompose readily?

 AJELIAS L7-S12
-Hydride elimination

Beta-hydride elimination is a reaction in which an alkyl group having a hydrogen,

bonded to a metal centre is converted into the corresponding metal-bonded
hydride and a bonded alkene. The alkyl must have hydrogens on the beta carbon.
For instance butyl groups can undergo this reaction but methyl groups cannot. The
metal complex must have an empty (or vacant) site cis to the alkyl group for this
reaction to occur.

No change in the formal oxidation state of the metal

mechanism
H H H H H
H H H
C H C C
M
M C M C C
H H H H H H

Can either be a vital step in a reaction or an unwanted side reaction

 AJELIAS L7-S13

-hydrogen elimination does not happen when

the alkyl has no -hydrogen (as in PhCH2, Me3CCH2, Me3SiCH2)
(ii) the -hydrogen on the alkyl is unable to approach the metal (as in
CCH)
the MCCH unit cannot become coplanar

Select the most unstable platinum complex from the given

list. Justify your answer

H
Ph3P C Ph3P Ph3P
SiMe3 Et3P C
Pt Pt Pt Pt
Ph3P SiMe3 Ph3P Ph3P
Et3P C
C
H
A B C D

No -H -H unable to MCCH unit will not be

approach M coplanar
 Problem solving

Classify the following reactions as oxidative addition,

reductive elimination, (1,1 / 1,2)migratory insertion, - H
elimination, ligand coordination change or simple addition

(a) [RhI3(CO)2CH3] {RhI3(CO)( solvent)[C(O)CH3]}

(b) Ir(PPh2Me)2(CO)Cl + CF3I Ir(I)(CF3)(PPh2Me)2(CO)Cl

(c) TiCl4 +2 Et3N TiCl4 (NEt3)2

(d) HCo(CO)3(CH2=CHCH3) + CO CH3CH2CH2Co(CO)4

Step 1. determine the oxidation state of the metal in reactant and product
Step 2. count the electrons for reactant and product
Step 3. see if any ligand in the reactant has undergone change
 AJELIAS L7-S14
Homogeneous catalysis using organometallic Catalysts

A catalyst typically increases the reaction rates by lowering the activation energy
by opening up pathways with lower Gibbs free energies of activation (G).
Gibbs energy of activation

uncatalyzed
Gibbs Energy

catalyzed

stable intermediate

Reactants Products

Heterogeneous Homogeneous
 Homogeneous versus Heterogeneous Catalysis

Parameter Heterogeneous Homogeneous

Phase Gas/solid Usually liquid/ or solid
soluble in the reactants
Required temperature High Low ( less than 250C)
Catalyst Activity Low High
Product selectivity Less (often mixtures) More
Catalyst recycling Simple and cost effective Expensive and complex

Reaction mechanism Poorly understood Reasonably well understood

Product separation Easy Elaborate and sometimes
from catalyst problematic
Fine tuning of catalyst Difficult Easy
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Heterogeneous Catalyst- Catalytic Converter of a Car

Platinum and
Palladium

Platinum and
Rhodium

Chemistry at the molecular level Poorly understood

Home assignment : See Youtube video Catalysis
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Comparing different catalysts; Catalyst life and Catalyst efficiency

Turnover Number (TON)

TON is defined as the amount of reactant (in moles) divided by

the amount of catalyst (in moles) times the percentage yield of
product. A large TON indicates a stable catalyst with a long
life.

Turnover Frequency (TOF)

It is the number of passes through the catalytic cycle per unit time
(often per hour). Effectively this is dividing the TON by the time
taken for the reaction. The units are just time1 . A higher TOF
indicates better efficiency for the catalyst
 AJELIAS L7-S17

Wilkinsons Catalyst for alkene hydrogenation

RhCl3 (H2O)3 + RhCl(PPh3)3 +

CH3CH2OH + CH3CHO +
3 PPh3 2HCl + 3H2O

Wilkinsons catalyst: The first example of an effective and rapid

homogeneous catalyst for hydrogenation of alkenes, active at room
temperature and atmospheric pressure.
Square planar 16 electron d8 complex (Ph3P)3RhCl
Discovered by G Wilkinson as well as by R Coffey almost at the same
time (196465)
Conventional Catalytic cycle for hydrogenation with Wilkinsons catalyst
P P
Rh
P Cl
P P The first step of this
P catalytic cycle is the
reductive Cl Rh H2 oxidative cleavage of a PPh3 to
elimination 14e P addition generate the active
form of the catalyst
RCH2CH3 followed by oxidative
addition of dihydrogen.

R H H
CH2
P P
H2C Rh H Rh
P P
Cl Cl

R
1, 2 -migratory alkene
insertion
P coordination
H H
Rh P = PPh3
P Cl