There are two possible pathways for the substitution

of a ligand in the octahedral complexes:

1- The Dissociative Mechanism (D Mechanism):
the bond between the substituted ligand and the metal ion is completely
ruptured and a five-coordinate intermediate occurs. This step is slow,
and the rate of reaction can be determined. The slow step is then
followed by a fast step where the coordinated deficient intermediate
captures the incoming ligand. This type of mechanism is called a
unimolecular nucleophilic substitution SN1.

2- The Associative Mechanism (A Mechanism):

In these reactions, the incoming ligand is completely bonded to the
metal ion to form a seven-coordinate intermediate in a slow step
followed by a fast one to lose the outgoing (leaving) ligand. This
mechanism is called bimolecular nucleophilic substitution SN2.
Examples for different substitution Reactions of
Octahedral Complexes:
1- Dissociative Reactions:
Suppose we have a complex with the type [MX4AB] and the ligand B
will be substituted by a ligand Y. When the reaction proceeds in
dissociative process, the complex will dissociate first as:

The five-coordinate intermediate [MX4A] will have either square

pyramid or trigonal bipyramid structure. In the square pyramid
intermediate, the ligand Y will enter the same place previously occupied
by the ligand B. Thus, the position of ligand Y with respect to A (cis or
trans) will be the same as the leaving ligand B. That means that the
arrangement of ligands in the formed product remains the same around
the central metal ion as in the reacted complex. The trans complex will
form a trans product and the cis complex will form a cis derivative.
These reactions are called dissociative reaction without structure
change.
If the intermediate is trigonal bipyramid, formed either from trans or cis
reactant, the attack of Y on such intermediate will result in the formation
cis and trans products from the trans complexes. It is found that 66.6 %
of the product is cis and 33.3 % trans are formed.

2- Associative Reactions:
In these types of reactions, a pentagonal bipyramid seven coordinate
intermediate is formed. When the incoming ligand Y is approached the
[MX4AB] complex, it may enter from the trans site of the leaving group
B (trans attack) or enter from the cis site of the group B (cis attack). If
the reacting complex is trans, the trans attack will give cis product and
the cis attack will result in a trans derivative.
On the other hand, if the starting complex is cis, the product will depend
on the type of attack. In case of cis attack, the product will be cis. In
case of trans attack, a mixture of cis and trans will form.

Anation Reactions:
In these reactions, the incoming ligand is an ion such as substitution of
ammonia molecule by a bromide ion in an aqueous solution.
[Co (NH3)6]3+ + Br- [Co (NH3)5Br]2+ + NH3
Aquation:
In these reactions, substitution of a coordinated ion X- by a water
molecule is occurred.

The Trans Effect:

The trans effect is best defined as the effect of a coordinated ligand
upon the rate of substitution of ligands opposite to it.
The following two examples about trans effect:

We find that the C2H4 group activate the trans position more than the cis
one and consequently the chloride ion in the trans position is substituted
by ammonia molecule.
The trans effect is used in modifying new methods for
preparation of different compounds.
For example, the preparation of cis and trans [Pt (NH3)2Cl2] complex.
The cis isomer can be prepared from the reaction of [PtCl4]2- with
ammonia. Since Chloride ion has larger trans effect than NH3.

The trans isomer is prepared from the reaction of [Pt (NH3)4]2+ with Cl-.
Again, since Cl- has a greater trans effect than NH3, the substituted
chloride will go to the trans position of the first substituted chloride.

Electron transfer reactions can be divided into two

categories:
a) Electron transfer without any chemical change. It thus called electron
transfer processes.
b) Electron transfer including chemical change. This type of electron
transfer is known as normal oxidation reduction processes.
In electron transfer reactions there are two mechanisms:
- outer sphere mechanism.
- inner sphere mechanism.
Outer Sphere Electron Transfer:
In principle, all outer sphere mechanisms involve electron transfer from
a reductant to an oxidant with the coordination shells or spheres of each
staying intact.

As can see from the above example, these reactions proceed without a
chemical change.
Inner Sphere Electron Transfer:
An inner sphere mechanism is the one in which the reductant and
oxidant share a ligand in their inner or primary coordination spheres,
and the electron being transferred across a bridging group formed in the
intermediate. For example

The following are some ligands which can act as a bridging ligand in
this reaction:
X = F-, Cl-, Br-, I-, SO42-, NCS-, N3-, PO43-, P2O74-, CH3COO-,
C3H7COO-, crotonato, succinato, oxalato.
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 centre must have two electrons at least in the d orbital
(d2 at least) where the formal oxidation state increases by +2.
b) The metal centre 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).

* Oxidative addition reactions with bimolecular complexes

Reductive Elimination Reactions:

The reverse reaction of the oxidative addition reaction is called
reductive elimination reaction. These reactions can be configured from
the following equilibrium:
From the examples of the reductive elimination reactions are the
elimination of alkane, aldehyde, alkyl halide, etc.

General Features of Reductive Elimination Reactions:

a) The reaction can proceed when there are two groups in cis position
can be eliminated.
b) The metal ion should have higher oxidation state.
c) The electron-rich metal ion cannot undergo elimination reactions.
Insertion Reactions:
Insertion reactions involve the insertion of an unsaturated ligand (X)
into an adjacent M-X bond in the same complex, as can be represented
by the equation:
The final resultant of the reaction is the decrease of the coordination
number by one with the formation of a new bond (X-Y). The reverse
reaction for the insertion reaction is called deinsertion reaction.
General Features of Insertion reactions:
a- There is no change in the formal oxidation state of the metal ion
before and after the reaction.
b- The groups must be adjacent (cis) to each other.
c- A vacant coordination site is created during the forward reaction
(insertion reaction).
d- If the inserted group X has a chiral centre, the reaction proceeds
without change of the stereochemistry of the group (retention of
configuration).
e- The equilibrium of the reaction depends on the strength of M–X, M–
Y and M–(XY) bonds.
f- The rate of the reaction is usually increased if the reaction is
accompanied by one electron oxidation process.

Mechanism of the insertion reactions:

In case of the insertion of a CO group in a bond between a metal atom
and a metal alkyl bond, the reaction can be proceeded in two ways.
Either the alkyl group migrates to a carbonyl group (alkyl migration), or
a CO group inserts into a metal alkyl bond (CO insertion).
Homogeneous catalysts are those which exist in the same phase (gas or
liquid) as the reactants, while heterogeneous catalysts are not in the
same phase as the reactants.

Catalytic Homogeneous Olefin Hydrogenation Reactions:

General reaction:

Wilkinson's catalyst is an example of the catalysts used in

hydrogenation reactions.