Structure and Bonding in Monoolefin Complexes

The coordination of a mono-olefin to a transition metal provides the simplest

example of a metal -complex

The qualitative bonding description is similar to that for the M-CO moiety as
far as the donor-acceptor synergism is concerned

σ-donation π-back donation

The donor component is the interaction of the (a) filled -bonding orbital of
ethylene with vacant metal orbitals and (b) the acceptor component is that of the
filled metal orbitals with the vacant *-antibonding orbital of ethylene
Complexes between metal salts and alkenes have been known since 1827 but they were not
understood until the later half of the last century (year 1975). Zeise’s salt is prepared from
the reaction of C2H4 and K2PtCl4

Silver ions form similar alkene complexes which are soluble in aqueous solution. Catalysts
for the polymerization of alkenes also form metal-alkene complexes which leads to
polymerized product

Pt

CH2=CH2

[PtCl3(C2H4)]-
 coordination of an ethylene
ligand with a transition metal Relative to free ethylene (1.337 Å), the C-C
bond (1.37 Å) is lengthened slightly
The extent of back bonding depends on

a) the metal
b) the substituents on ethylene
c) the other ligands on the metal

The -accepting ability of the alkene ligand significantly influences the metal-
carbon bonds in these compounds

In cases such as [Pt(Ph3P)2(CH2=CH2)] the metal is very

electron rich.  back donation is significant and as a result
the C-C bond of the alkene lengthens considerably and the
hydrogens are bent out of plane

This compound may be viewed as a

metallacyclopropane. We can consider the
extreme bonding situations namely 
donation and metallacycle as resonance
structures
Reaction chemistry of organometallic complexes

1. Reactions involving the gain and loss of ligands

a. Ligand Dissociation and Association

b. Oxidative Addition
c. Reductive Elimination

2. Reactions involving modifications of the ligand

a. Insertion
b. Carbonyl insertion (alkyl migration)
 Ligand dissociation/association

• Electron count changes by -/+ 2

• No change in oxidation state

• Dissociation easiest if ligand is stable on its own

(CO, olefin, phosphine, Cl-, ...)

• Steric factors important

Dissociation

M M + Br-
Br
Association
 Oxidative Addition

When addition of ligands is accompanied by oxidation of the metal, it is called

an oxidative addition reaction

✓ Oxidation state of the metal increases by 2 units

✓ Coordination number increases by 2 units
✓ 2 new anionic ligands are added to the metal
Requirements for oxidative addition:

✓ availability of non-bonded electron density on the metal

✓ Two vacant coordination sites on the reacting complex (LnM) - the complex
must be coordinally unsaturated

✓ a metal with stable oxidation states separated by two units; the higher
oxidation state must be energetically accessible and stable

Factors affecting the ease of oxidative addition:

o The ease of oxidation (usually d8 to d6 with formal loss of two electron)

o the relative stability of coordination number 4 compared to 6

o the strength of new bonds created (compared to ones before) are key
determinants

o Oxidative addition is more likely for low-valent metals. The ease of

oxidation is Co(I) < Rh(I) < Ir(I) (increases from top to bottom)
One reaction multiple mechanisms

Concerted addition, mostly with non-polar X-Y bonds

H2, silanes, alkanes, O2, ...

X X X
LnM + LnM LnM Intermediate A is called
Y Y Y as a σ-complex
A

Reaction may stop here if metal-centered lone pairs are not readily available

Final product is expected to have cis - X,Y groups

Stepwise addition, with polar X-Y bonds

– HX, R3SnX, acyl/allyl halides, ...

– low-valent, electron-rich metal fragment (IrI, Pd(0), ...)

X
LnM X Y LnM X Y LnM
Y
B

polar media favors this transition state (B)

Metal initially acts as nucleophile

– Coordinative unsaturation less important

• Ionic intermediate (B)

• Final geometry (cis or trans) not easy to predict
• Radical mechanism is also possible
Examples of Oxidative addition : cis or trans

Homonuclear systems (H2, Cl2, O2, C2H2) – cis

Heteronuclear systems (MeI) – cis or trans
An important step (often the 1st) in many homogenous catalytic cycles

Hydrogenation of alkenes – Wilkinson catalyst

Cis-addition

Methanol to acetic acid conversion – Cativa process

CH3I

Pd catalyzed Cross coupling of ArB(OH)2 and Ar-X – Suzuki coupling

The more electron rich is the metal, more easy is the oxidative addition
 Reductive Elimination

Almost the exact reverse of Oxidative Addition

• Oxidation state of metal decreases by 2 units

• Coordination number decreases by 2 units
• 2 cis-oriented anionic ligands form a stable σ-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
✓ An electronically stable organic product

The groups taking part in reductive elimination MUST be in cis orientation

 Final step in many homogenous catalytic cycles

Hydroformylation (conversion of an alkene to an aldehyde)

RCH2CH2CHO

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

Cativa Process (Methanol to Acetic acid)

 Migratory Insertion

• 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
• cis-orientation of the groups undergoing migratory insertion is MUST

These reactions are enthalpy driven

 Types of Migratory Insertion

If a metal center has a σ-bound group (hydride, alkyl, aryl) and a ligand
containing a π-system (olefin, alkyne, CO) the σ-bound group can migrate to
the π-system

[For CO, RNC

(isonitriles)]

(For Olefins)

R
M M M M
R R R
 Migration vs. Insertion

There are two different directions that a migratory insertion can occur

Migration: when the anionic ligand moves and performs a nucleophilic-like

intramolecular attack on the electrophilic neutral ligand

Insertion: when the neutral ligand moves and inserts into the bond between the
metal and anionic ligand

Migration Insertion

Mn(+1) Mn(+1) Mn(+1) Mn(+1)

18e- 16e- 18e- 16e-
 Is this a migration or insertion process?

migration

L = Solvent ligand

insertion
 insertion

Infrared studies with 13CO have revealed that the reaction proceeds by
migration of the methyl ligand rather than by CO insertion
 Catalysis and Organometallics

An attractive approach to increase the rate of the reaction is to employ a catalyst

Catalysts are classified as homogeneous if they are soluble in the reaction

medium and heterogeneous if they are insoluble

Heterogeneous:
Easy to separate product from catalyst
Preferred for industrial application
Drawback: Tend to have low selectivity/specificity

Homogeneous:
More selective
Milder conditions
Easier to study, modify, optimize
Drawback: Difficult to separate product from catalyst

Many important compounds are produced commercially using organometallic

homogenous catalysts
 Catalysis and Organometallics

Fundamental concepts:

Ea (uncatalyzed) > Ea (catalyzed)

Catalyst are not reagents. They enter into the

mechanism but not into the overall reaction
equation

TON (turnover number) : (Moleproduct/molecat)

Total number of moles of product / mole of catalyst

TOF (turnover frequency) : TON/time =

(Moleproduct/time.molecat)

Catalytic cycle: a cycle of reactions that comprise the reaction mechanism,

always returning the catalyst to its original form
 Alkene Hydrogenation

CH2=CH2 + H2 → CH3– CH3

The first effective homogeneous catalyst discovered for such a reaction is the
famous Wilkinson’s catalyst (Ph3P)3RhCl

Hydrogenation generally
results in syn-addition which
Rh P implies a concerted H-transfer
P mechanism.
P
Cl

Some cases trans-products are also formed; in such cases a radical mechanism is
involved or there is a subsequent isomerization step to the more stable trans-
product
Hydrogenation
CH2=CH2 + H2 → CH3– CH3

Wilkinson’s catalyst
(Ph3P)3RhCl

CH2CH2R

CH2CH2R
 Alternative mechanism

Ligand dissociation

Since this tri-coordinated Rh is

very reactive, although present
RCH2CH3 in small amount, involvement
in the reaction mechanism
can’t be neglected

R
R
 Alkene Hydrogenation

o Wilkinson’s catalyst is highly sensitive to the nature of the phosphine

ligand and the alkene substrate

o Analogous complexes with alkyl-phosphine ligands are inactive,

presumably because they are more strongly bound to the metal atom
and do not readily dissociate to complete the catalytic cycle

o Similarly, the alkene must be just the right size: highly hindered alkenes
or the sterically unencumbered ethene are not hydrogenated by the
catalyst

o presumably because the sterically crowded alkenes do not coordinate

and ethene forms a strong complex that does not react further
 Alkene Hydrogenation

Relative reactivity of alkenes for homogenous catalytic hydrogenation

o Cis-alkenes undergo hydrogenation more readily than trans alkenes

o Internal and branched alkenes undergo hydrogenation more slowly than
terminal ones
 Hydroformylation

Hydroformylation (oxo process) was discovered by Roelen in 1938 and is

the oldest and largest volume catalytic reaction involving alkenes

The conversion of propylene to butyraldehyde is the most important

application

The reaction of an alkene with CO and H2 catalyzed by Co or Rh salts is

called hydroformylation

Overall Reaction: RCH=CH2 + CO + H2 → RCH2CH2CHO

In a formal sense, a H atom and a formyl group are added across a double
bond, hence the name hydroformylation. As a result, the carbon chain is
increased by one
 Over all Reaction: RCH=CH2 + CO + H2 → RCH2CH2CHO

[Co2(CO)8] + H2 → HCo(CO)4
-CO

Reductive
1,1
elimination

Oxidative
1,1addition 1,2-migratory
1,1 insertion

(CO)3Co-C(=O)(CH2)2R

1,1 insertion
1,1-migratory
 Monsanto acetic acid process

Large quantities of methanol can be produced from synthetic gas

Methanol can be easily converted to other commercial products like

acetic acid, formaldehyde and gasolene

The conversion of methanol to acetic acid can be done by using

Monsanto acetic acid process
 Monsanto acetic acid process

➢ This is another carbonylation reaction introduced in early 70’s by

Monsanto

➢ This reaction involves dual catalysis with HI and salts of [RhI2(CO)2]- anionic
complex
Monsanto acetic acid process
Monsanto acetic acid process
 Wacker process

Steps involved:

CH2=CH2 + PdCl2 + H2O → CH3CHO + Pd(0) + 2 HCl

Pd(0) + 2 CuCl2 → PdCl2 + 2 CuCl

2CuCl + 2HCl + ½ O2 → 2 CuCl2 + H2 O

_____________________________________________

Net Reaction:
CH2=CH2 + ½ O2 → CH3CHO
Wacker process