Inorganic Reaction Mechanisms

By
Prof. Ramadan M. Ramadan
http://rmramadan-notes.pbworks.com
Oxidative Addition and Reductive Elimination Reactions

Oxidative Addition Reactions:

 The general equation for this reaction is:

 There are some conditions should be satisfied to carry out these reactions:
 a) The metal center must have two electrons at least in the d orbital (d2 at
least) where the formal oxidation state increases by +2.
 b) The metal center must be coordinatively unsaturated and
can increase its coordination number by 2.
 c) The metal must have appropriate vacant orbitals to
accommodate the added ligand electrons.
 Some examples are:
 ** Addition of hydrogen to an iridium complex (example for a
transition metal).

 ** Formation of a Grignard reagent from magnesium, phosphorus

pentafluoride and tin tetrachloride (examples for main group
compounds).
 ** The thermal effect on an iridium complex (an example for
intramolecular oxidative addition reaction).
 These reactions are called orthometallation reactions.

 ** Oxidative addition reactions with bimolecular complexes.

 ** Oxidative addition reactions accompanied with C-H activation (carbon-
hydrogen bond activation).
 In the present example, the reaction of C6H6 derivative undergoes faster than
CH4 derivative although the Ph-H bond is stronger than CH3-H bond.
 This is because the intermediate formed in the C6H6 derivative can not be
formed in case of CH4 derivative.
Kinetic Rate Laws for Oxidative Addition Reactions

a) The d8 Square planar Complexes:

 Example is the oxidative addition of X-Y to IrCl(CO)(PPh3)2
(Vaska's complex).

 The rate law can be given by:

R = k2 [Ir(I)] [XY]
 From the rate equation, it can be noted that the reaction is
bimolecular and from reaction equation the iridium complex is
coordinatively unsaturated system.
Kinetic Rate Laws for Oxidative Addition Reactions

b) The d8 Trigonal Bipyramidal Complexes:

 Example is the oxidative addition of X-Y to IrH(CO)(PPh3)3
complex:
 The reaction has a characteristic of coordinatively
saturated complexes and is consistent with the following
scheme,

 Note: The reaction is retarded by extra phosphine.

Mechanisms of Oxidative Addition Reactions
 There are three main mechanisms have been observed depending on the
reactants and conditions of reaction.
A- The Concerted Mechanism:
 The characteristics of this mechanism are:
 a) The reaction involves a 3-centre transition state with a side on approach of
the incoming molecule.
 b) The molecule X-Y attaches to the reaction center and simultaneously or
subsequently undergoes electron rearrangement from X-Y bond to M-X and M-
Y bonds, i.e.,
 The Features of the Concerted Mechanism:
 a- The molecule is coordinatively unsaturated.
 b- The reaction is common when the X-Y group has a low bond
polarity such as H2 and R3Si-H molecules.
 c- The reaction is stereospecific and cis-addition of X-Y occurs.
 Example:

 From the infrared spectroscopy studies, the cis addition is

shown by observing 2 M-H stretching bands (symmetric and
asymmetric).
 Note: If the formed product is trans, only one asymmetric
stretching band is observed.
 d- If X-Y is a chiral ligand, the reaction proceeds with a
retention of configuration, e.g.,

 e- The side on addition of H2 molecule is found to have low

activation energy (ΔG‡ = 40 kj.mol-1).
 f- The rate of addition of H2 to Vaska's complex for example
depends on the type of X.

 g- The electron density on the metal center is important in

determining the activation energy (ΔG‡).
 Also, the most important factor in the addition of hydrogen is
the donation into H2(σ*).
Mechanisms of Oxidative Addition Reactions
B- The Oxidative Addition with Nucleophilic Attack:
 These reactions are characterized by some factors:
 a) They are favored when the X-Y bond is polar, e.g., RX, HX, HgCl2.
 b) The transition state is expected to be dipolar.
 In this case, the metal center acts as an electron pair donor, i.e., acts as a nucleophile.

 c) For reactions involving addition of a chiral R-X compound, reaction proceeds with
inversion of the stereochemistry at the α- carbon.
 For example,
 The features of nucleophilic Attack:
 a- The addition to the complex is from the trans
positions.
 b- The rate of the reaction is faster in polar
solvents.
 c- The reaction has a large negative ΔS‡ due to
solvent organization around the dipolar transition
state.
 d- The rate of the reaction is sensitive to the
nature of the other ligands (L).
 Example:

 From the characteristic features of the above reaction:

 a) As the electron donating property of the phosphine increases, the rate of
addition increases.
 b) The increased ligand basicity leads to increased nucleophillicity of the Ir
center.
 c) By increasing the size of ligands, the rate of oxidative addition decreases
due to the crowding of transition state (steric effects).