Molecular Orbital Diagram of CO

pσ*
pπ*
In carbon monoxide, the
bonding orbitals reside
more on the oxygen atom,
sσ*
pπ and the anti-bonding
orbitals reside more on the
carbon atom.
pσ
sσ
 M-CO Bonding

Carbon monoxide bonds to transition metals using "synergic π*-

back-bonding." The bonding has three components, giving rise to a
partial triple bond. A σ-bond arises from overlap of nonbonding
electron pair on carbon with a blend of d-, s-, and p-orbitals on the
metal. A pair of π bonds arises from overlap of filled d-orbitals on
the metal with a pair of π-antibonding orbitals projecting from the
carbon of the CO. The latter kind of binding requires that the metal
have d-electrons, and that the metal is in a relatively low oxidation
state (<+2). The π-bonding has the effect of weakening the C–O
bond compared with free carbon monoxide.
 M-C2H4 Bonding
The π-acid alkene donates electron density into a metal d-orbital
from π-symmetry bonding orbital between the carbon atoms (I).
The metal donates electrons back from (a different) filled d-orbital
into the empty π* antibonding orbital (II).

Both of these effects tend to reduce the carbon-carbon bond order,

leading to an elongated C-C distance and a lowering its vibrational
frequency.

In pound Ni(CH2CH2)(PPh3)2 the value is 143 pm.

Reactions:
Oxidative Addition, Reductive Elimination,
Insertion and β-Hydride Elimination
Oxidative addition and reductive elimination are two important and
related classes of reactions in organometallic chemistry. Oxidative addition is a
process that increases both the oxidation state and coordination number of a metal
centre. Oxidative addition is often a step in catalytic cycles, in conjunction with its
reverse reaction, reductive elimination

For transition metals, oxidative reaction results in the decrease in the dn to a

configuration with fewer electrons, often 2e fewer. Oxidative addition is favored for
metals that are (i) basic and/or (ii) easily oxidized. Metals with a relatively low
oxidation state often satisfy one of these requirements, but even high oxidation state
metals undergo oxidative addition, as illustrated by the oxidation of Pt(II) with
chlorine:
[PtIICl4]2− + Cl2 → [PtIVCl6]2−
The resulting ligands will be mutually cis, although subsequent isomerization may
occur.
• Reductive elimination, the reverse of oxidative addition,
is most often seen in higher oxidation states because the
formal oxidation state of the metal is reduced by two
units in the reaction.
Hydrogenation of olefin: RCH=CH2 + H2  RCH2CH3
Cl PAr3
Rh
Ar3P PAr3
S ligand dissociation
PAr3
CH3CH3
Ar3P S H-H
reductive Rh
elimination Cl PAr3 oxidative
addition
irreversible

H H
Ar3P CH2CH2H Ar3P H
Rh Rh
Cl PAr3 Cl PAr3
S S
insertion/
migration H
rearrangement Ar3P H substrate
Rh coordination
Cl PAr3
S S