REACTIVITY OF METAL COMPLEXES

Substitution Reactions
Substitution reactions are those reactions in which an attacking ligand replaces previously attached ligand
to substrate.
The ligand that departs from complex is called leaving group, and the group which takes the position of
leaving group is called attacking or substituting group.
Substitution reactions in octahedral complexes
Substitution reaction involves supplement of one ligand by other. Since ligand can be treated as negative
point charge or dipole, they are assumed to have nucleophilic character. Therefore the substitution reaction
that results by replacement of one ligand by other is called nucleophilic substitution (SN) reaction.
For example

The attacking ligand can attack on substrate MX6 by several ways to produce MX5Y.
There are Three possible mechanisms.
(i) Unimolecular Nucleophlic Substitution (SN1) or dissociative SN1 mechanism
(ii) Bimolecular Nucleophlic Substitution (SN2) or associative SN2 mechanism
(iii) Interchange reaction: Dissociative Nucleophilic Substitution reaction (ID) and Associative
Nucleophilic Substitution reaction (IA).
(i) SN1 Mechanism:
This mechanism involves two step processes. In the first step complex first undergoes dissociation and
looses a ligand to produce a 5-coordinated square pyramidal or trigonal bipyramidal intermediate complex
and in the second step the intermediate undergoes rapid combination with nucleophile.

The first step is slow and the second step is fast the rate of the reactions depends on the slow
step and given as Rate = K[ MX6]
Where, K is the rate constant of forward reaction in step 1.
Hence SN1 mechanism is first order reaction i.e when we consider its kinetic aspect, we can call it
unimolecular reaction.

In SN1 Nmechanism two types of intermediate can be formed

(i) The bond M-X dissociates causing least disturbance to the remaining five coordinated
intermediate which has a square pyramidal geometry. The intermediate [MX5] is then
 attacked by Y to produce [MX5Y] as shown below.

(ii) The bond M-X dissociates and the remaining [MX5], immediately adjusts the bond angles
to produce a trigonal bipyramidal intermediate which is then attached by Y to produce
[MX5Y] as given below.

Since, TBP intermediate needs movemdent of two bonds whereas no such movement is required
during the formation of SP intermediate hence SP intermediate is generally formed in
SN1mechanism. However, SN1 reaction proceeds through a TBP intermediate, where formation of
π-bond is possible

(ii) SN2 Mechanism: In this mechanism new ligand first adds on tothe complex to from a seven
coordinated activated complex or intermediate complex which then readily undergoes
association. So, this is also a two step process.

In this case the reaction rate depends upon the first step i.e. upon the concentration of the complex
of well as the concentration of the incoming ligand Y.
Rate = k[MX6][Y]
Hence, SN2 mechanism is second order reaction and is bimolecular. However, when solvent itself
acts as nucleophile for example H2O, alcohol etc., and reaction shows first order
behaviour(pseudo first order).

In SN2 mechanism two types of intermediate can be formed.

(i) The nucleophile Y attacks on the one of the edges of the octahedron forming a pentagonal
bipyramidal (PBP) intermediate as shown below.
 (ii) The nucleophile Y attacks through the middle of one of the triangular faces of the octahedron
forming a octahedral wedge intermediate, in which both attacking group Y and leaving group
X are present in equivalent position as shown below.

Since PBP required movement of four ligands to adjust the incoming nucleophile this increases
energy of PBP intermediate, while OW requires minimum movement of ligands that’s why the
ligand-ligand repulsion are less in OW than in PBP. This indicates that SN2 reaction preferably
proceeds by OW intermediate.

(iii) Interchange reaction: If ligand first attacks to the substrate and form ion pair, before breaking
of leaving group from metal complex specie. Then the reaction is called an interchange reaction.
If degree of assistance of assistance of nucleophile is small and reaction primarily undergo
dissociation pathway, then the reaction is called dissociative Interchange (ID). While, if reaction
is more tilted towards association reaction, then the reaction is called associative Interchange
reaction (Ia).
[MX6] + Y [X5MX.Y]

Inert and Labile Complexes:

Under the fixed condition of concentration of substrate of 0.1M and temperature 25°C,
complexes that undergo quick displacement (t½< 1.0 minute) of one ligand by other are
called labile complexes.
Under the fixed condition of concentration of substrate of 0.1M and temperature 25°C,
complexes that undergo slow displacement (t½> 1.0 minute) of one ligand by other are
called inert complexes.
Example:
-
[Fe(H2O)6]3+ + SCN → [Fe(H2O)5(SCN)]2+ + H2O
Labile complex(t½<1 min)
 - -
[Cr(CN)6]3- + 6 14CN → [Fe(14CN)]3- + 6 CN
Inert complex(t½=24 days)

Substitution reactions in Square Planar Complexes

The complexes of d8 configurations are in general occupy a four-coordinate square planar
geometry. In general, the kinetic studies in square planar complexes has been carried out on the
Pt(II), Ni(II), Pd(II), Rh(I), Ir(I) and Au(III) complexes. However, the most extensive work has
been done on Pt(II) d8 Complexes because
They are easily synthesised
The complexes formed are stable
Their rates of reactions are slow.
The mechanism of substitution reactions of square planar complexes appears to be
associative SN2 rather than dissociative SN1.

The rate equation indicates that the complex [Pt L2T X] is reacting in two different path ways.
1.Solvent path

2.Reagent path (Direct path)

The reaction rate is given by
Rate = k1[Pt L2T X] + k2[Pt L2T X] [Y]
This indicates that the rate determining step is bimolecular and the mechanism involved is
associative SN2 mechanism.

Stereochemistry
Ligand Substitution occurs with retention of configuration. i.e. cis complex yields cis-product and trans
complex yields trans-product. Thus, the substitution reaction is entirely stereospecific.

Stereospecificity is possible with a trigonal bipyramidal intermediate containing the entering ligand,
leaving ligand and trans ligand in the trigonal plane. This is a strong evidence for associative type (SN2)
mechanism.

Factors affecting the rates of substitution reactions in SPL complexes

1.Effect of entering group (Y)

2.Effect of leaving group (X)
3.Steric effect of other groups
4.Solvent effect
5.Trans effect
 Trans effect
Trans effect was studies by Chernuyaev (1926) to understand the kinetic behavior of a planner
complex.

Def: The effect of a ligand over rate of substitution of another ligand positioned trans to it in
the square planar complexes.

Since Cl- has greater Trans effect than NH3, hence Cl- opposite to NH3 do not replaced.

Since C2H4 has greater Trans effect than Cl-, hence Cl- opposite to C2H4 is replaced.
The group that directs the substitution trans to it, called as trans directing group. The trans effect is
a kinetic phenomenon.
Langford and Gray find out a series of ligands for trans directing ability. The series is
CN- = Co = NO= C2H4>SC(NH2)2 = H- = PR3> I- = SCN->Cl->Py> RNH2> NH3> OH-> H2O
There are two theories to explain trans effect.
1. Polarization theory:
According to this theory the polarization (effect of σ-bonding) of a ligand would be
directly related to its Trans effect. In case of [PtL2(X)2] type complex, two ligands X
and L are opposite (trans) to each other, their dipole do not cancel each other. Due to
larger size, L has higher polarizability than X. The induced dipole of L causes
deformation in Pt (II), results more effective bonding and higher bond energy in L-Pt
than Pt-X trans to it. This results Pt-X bond trans to Pt-L bond are weaken and longer.
The weakening of Pt-X bond trans to Pt-L causes the rate of substitution of X more
easily. It is evident that due to higher polarizability, L has higher trans effect than X.

The Trans effect of the ligands increases with the increase of their polarizability.
e.g. Cl-< Br-< I- Polarizability increases and hence trans effect increases.
2. Π -bond theory

The ligands having vacant  or * orbitals can accept electron from filled metal orbital to form
metal-ligand -bond (d-d or d-p bond). These ligands are therefore called -bonding
ligands for example CO, CN-, C2H4, PR3 etc. The Trans directing ability of the -bonding
ligands increases with the increase of their ability to form metal–ligand - bond.

The formation of the π-bond increases the electron density on the Pt-L bond and decreases on
Trans of L. These results the Pt-X bond trans to Pt-L bond weaker; hence substitution goes to
X trans to L.
Let T be the trans-directing group, L as the leaving group and E as the entering group. The
entering ligand binds to 16-electron Pt(II) complex to form 18-electron complex which in turn
again converted into a new 16-electron complex.

The entering ligand always sits at the equatorial position of the activated complex which is
trigonal-bipyramidal in nature. The trans-directing group and the leaving group are pushed down to
create the equatorial plane of theactivated complex.

Applications

1. Synthesis of the cis and trans isomers: The two isomers can be synthesized via a number of
chemical routes by exploiting the trans effect.

cis-[Pt Cl2 (NH3)2]is obtained by treating [Pt Cl4]2-ion withNH3

Cis-Platin

trans-[Pt Cl2 (NH3)2]is obtained by treating [Pt (NH3)4]2+ion with Cl-

Trans-Platin
2. Differentiating between cis and trans isomers of [PtCl2(NH3)2]: A Russian scientist Kurnakov
has used the trans effect to distinguish between the cis and trans platin. The experimental route is
named as Kurnakov test.
The trans effect of thiourea is greater than chloride and amine ligands. The addition of thiourea
to the trans platin results in the replacement of trans chloride ions and the reaction stops.
However, when the thiourea is added to the cis isomer, all the four ligands are displaced and
[Pt(tu)4]2+ is formed.