Subject Chemistry

Paper No and Title 3 and Inorganic Chemistry-I (Stereochemistry,

Metal-Ligand Equilibria and Reaction Mechanism
of Transition Metal Complexes)
Module No and 35 and Cross Reactions and Marcus-Huss relation
Title
Module Tag CHE_P3_M35

CHEMISTRY Paper 3: Inorganic Chemistry-I (Stereochemistry, Metal-Ligand

Equilibria and Reaction Mechanism of Transition Metal
Complexes
Module35:Cross Reactions and Marcus-Huss relation
 TABLE OF CONTENTS

1. Learning Outcomes
2. Introduction to cross reactions
2.1. Cross reactions
2.2. Marcus-Cross-Relation
3. Summary

CHEMISTRY Paper 3: Inorganic Chemistry-I (Stereochemistry, Metal-Ligand

Equilibria and Reaction Mechanism of Transition Metal
Complexes
Module35:Cross Reactions and Marcus-Huss relation
 1. Learning Outcomes

 Basic information on cross electron transfer reactions

 Differences on rate and equilibrium constants for outer sphere reactions and cross
reactions
 Marcus relationship for cross reactions (how Marcus equation is applied for cross
reactions)
 Contribution of various type of free energies on electron transfer

2. Introduction to redox reactions or electron transfer reaction

2.1. Cross Reactions

Unlike to the outer sphere and inner sphere redox reactions, cross reactions demand the
reacting partners which are different to each other by more than the oxidation states. The
very common example chosen from numerous known reactions of this kind is reduction
of MnO4 by I to afford I2 and again MnO42. As far as cross reactions in metal
complexes are concerned, it requires one of the reacting complexes to be relatively inert
with respect to the other complex. It is deeply associated with self-exchange reactions
(please see Module No 28) with the distinction that cross reaction involves two different
metals. The general schematic representation is given below:

Moreover, the complex which is relatively inert in nature should not have a binding site
(non-bonding electron pair should be absent), otherwise it will react with the labile
partner. The reaction provided below represents cross reaction:

CHEMISTRY Paper 3: Inorganic Chemistry-I (Stereochemistry, Metal-Ligand

Equilibria and Reaction Mechanism of Transition Metal
Complexes
Module35:Cross Reactions and Marcus-Huss relation
 Although, replacing Cr(II) by V(II) from above reaction another cross reaction is
obtained where [V(H2O)6]2+ is not that labile like [Cr(H2O)6]2+.

Some other cross reactions are also given below:

The thermodynamic and kinetic data for a couple of self-exchange reactions are
compared with cross-reaction data by Marcus-Hush theory (please see previous
modules). The data for cross reaction lie between the two self-exchange counterparts.
Determination whether the reaction proceeds through an outer sphere mechanism is also
done on the basis of this theory.
The equilibrium constants for self-exchange type reactions are given as k11, K22 etc and
for cross reactions equilibrium constants are given as k12, K21 etc. Likewise, standard
Gibbs energy of cross reactions is denoted as ΔG°12, ΔG°21 etc.
For self-exchange reactions ΔG°= 0 whereas for cross reactions ΔG°≠ 0.
Gibbs free energy of activation (∆G♯) is symbolized by the equation given below:

 ∆wG# = Energy related to repulsion of ion in bringing the oxidant and reductant
partners close together

 ∆0G# = Energy related to the change in M-L bond distances

 ∆S∆GŦ= Energy related to the solvent rearrangements

CHEMISTRY Paper 3: Inorganic Chemistry-I (Stereochemistry, Metal-Ligand
Equilibria and Reaction Mechanism of Transition Metal
Complexes
Module35:Cross Reactions and Marcus-Huss relation
  T = Temperature (K)

 R = Gas constant

 K’ = Boltzman’s constant

 h = Planck’s constant

 Z = effective collision frequency in solution ~ 1011 dm3 mol-1 s-1

 ln ( k’T/hZ) = accounts for the energy lost in the formation of the encounter complex

2.2 Marcus-Cross-Relation
An equation was illustrated by Rudolph A. Marcus pertaining to the electron transfer as
well as for the calculation of associated rate constant. The basic hypothesis behind
deriving this equation is the solvation additivity and the vibration barrier of reacting
couples: Marcus equation which generally expresses the rates of outer sphere electron
transfer relating to free energy change is given by:

CHEMISTRY Paper 3: Inorganic Chemistry-I (Stereochemistry, Metal-Ligand

Equilibria and Reaction Mechanism of Transition Metal
Complexes
Module35:Cross Reactions and Marcus-Huss relation
 (K = equilibrium constant, k = rate constants, for the self-exchange reactions, f =
correction term for the free enthalpy differences between two educts. k11, k22, k12 and K12
can be acquired experimentally. Alternatively, k11 and k22 can be obtained theoretically
as:
k = κZ eΔG# /RT
K12 experimental·Ecell
Parameter f is generally close to 1 and is given by:

Wherein z is collision frequency

Most significant equation for one electron transfer process at RT (25 °C),

For such cross reactions, one order magnitude to the rate is contributed if E0 increases
by 0.12V.
The cross reaction deviates from outer-sphere mechanism and may signify other than
outer-sphere mechanism if calculated k12 value obtained from the abovementioned
equation corroborates with experimental value of k12.
The electron transfer barrier comprises two parts; i) the thermodynamic part (G12°) and ii)
the intrinsic contribution. The following equation represents activation of free energy for
electron transfer (G12‡):

Intrinsic thermodynamic contribution

CHEMISTRY Paper 3: Inorganic Chemistry-I (Stereochemistry, Metal-Ligand
Equilibria and Reaction Mechanism of Transition Metal
Complexes
Module35:Cross Reactions and Marcus-Huss relation
 As from the previous modules, it is evident that a bridging ligand that can serve as Lewis
base is the one most essential condition for inner sphere mechanism. However,
employing ambident ligands instead of normal Lewis base ligand one can differentiate
whether ligand attack is proximity or remote. Therefore, two separate mechanisms are
known for electron transfer through bridging/sharing ligands. 1) One step mechanism: it
involves redox reaction between the redox couples only); 2) Two step mechanism: It
involves bridging/sharing ligand in the redox or electron transfer reaction.
The activation of electron transfer reactions can be achieved either thermally wherein
lower energy complex is preferred or photochemically wherein higher energy complex is
preferred).
Given below is the example how to calculate the rate constant for cross reactions:

CHEMISTRY Paper 3: Inorganic Chemistry-I (Stereochemistry, Metal-Ligand

Equilibria and Reaction Mechanism of Transition Metal
Complexes
Module35:Cross Reactions and Marcus-Huss relation
CHEMISTRY Paper 3: Inorganic Chemistry-I (Stereochemistry, Metal-Ligand
Equilibria and Reaction Mechanism of Transition Metal
Complexes
Module35:Cross Reactions and Marcus-Huss relation
 3. Summary

 The fundamental understandings on cross reaction are obtained from introductory

section.
 The information obtained from equation illustrations how rate of cross reactions
can be obtained from self-exchange reactions.
 Marcus cross relationship equation helps to determine rate constant
 Contributions of diverse free energies on reorganizations of reactants is discussed
and summations of all free energy gives total energy of activation for cross
reactions

CHEMISTRY Paper 3: Inorganic Chemistry-I (Stereochemistry, Metal-Ligand

Equilibria and Reaction Mechanism of Transition Metal
Complexes
Module35:Cross Reactions and Marcus-Huss relation