SOME REACTION OF

ORGANOMETALLIC
COMPOUNDS
DR. NORSHAHIDATUL AKMAR BT MOHD SHOHAIMI
 Organometallic compounds undergo a rich variety of reactions,
which may involve loss or gain of ligands (or both), molecular
rearrangement, formation or breaking of bonds to the metal, or to
the ligands themselves.

a) Substitution Reaction in Carbonyl Complexes

A typical substitution reaction can be represented by the general
equation below:

This reaction represents an important way to introduce new

ligands into complexes.
This type of reaction does not involve any change in the formal
oxidation state of the metal center.
Although most substitution reactions proceed primarily by a
dissociative mechanism, an associative path is more likely for
complexes:
Having large metals (providing favorable sites for incoming
ligands to attack) and/or
Highly nucleophilic ligands

b) Insertion Reaction
Many reactions in organometallic chemistry involve
insertion of small molecules, X-Y, into metal-ligand bond,
especially M-C and M-H bonds.
Although some of these reactions are believed to occur by
direct, single-step insertion, many such reactions are much
more complicated and do not involve a direct insertion
step at all.
CO insertion
CO insertion - also known as carbonylation.
It was found that when CO reacts with an organometal
CH3Mn(CO)5, the product was (CH3CO)Mn(CO)5.
It seems that the CO has inserted itself between Mn-
CH3 bond to produce an acyl complex.
However, upon further investigation, when labeled
13CO was used, the product was found to be

(CH3CO)Mn(CO)4(13CO).
 The conclusions of this study are:
a) The inserted CO is one previously coordinated to the metal, not the
labeled one added to the complex. Therefore the CO that becomes the acyl-
carbonyl is not derived from external CO, but is one already coordinated to
the metal atom.
b) The incoming CO is added cis to the acyl group, as shown below.
c) Any other Lewis bases, L, can also bring about CO insertion, as shown in
the mechanism below. Therefore the conversion of alkyl into acyl can be
affected by addition of ligands such as PPh3 or any Lewis bases.
 The coordination number of the metal center increases in the
SO2 insertion reaction but it does not involve any changes in
the formal oxidation state of the metal center.
Therefore it is classified as a simple addition reaction.
When the increase in the coordination number is accompanied
by an increase in the oxidation number of the metal center, the
reaction is classified as an oxidative addition reaction.

c) Oxidative Addition (OA) Reaction

Low valence transition metal complex reacts with a molecule
XY to produce another complex with both the oxidation
number and coordination number of the metal increased.
Usually both the oxidation number and coordination number
of the central metal are increased by 2.
 For this reaction to occur the metal center must:
a) be d2 or greater.
b) be coordinatively unsaturated, i.e. can still accommodate
addition of 2 more ligands around it.
c) have less than 18 electrons. Compounds already having 18
electrons will not add more ligands because doing so will violate
the EAN rule.
d) have both appropriate and empty orbitals to accommodate
the donated lone pair of electrons.
 There is a decrease in the electron density on the metal as the
reaction proceeds which lowers the -backbonding from the
metal to the CO.
This effectively increases the bond order (hence strength) of
the C-O bond. This increase in the C-O bond strength is
reflected in the IR stretching frequency of CO, CO, from 1967
to 2075cm-1.
d) Reductive Elimination (RE) Reaction
The opposite reaction to oxidative addition is reductive
elimination where the opposite happens.
Both the oxidation number and coordination number of the
metal decreased with elimination of ligands as simple
molecules such as R-H, R-R, R-X and H-H where R,
R=alkyl, aryl; X=halogen.
An example of an RE reaction is: