Reaction mechanisms of Coordination Compounds: Electron Transfer Mechanisms

Advanced Inorganic Chemistry

Two general mechanisms

inner sphere donor and acceptor complexes share an inner sphere ligand in the transition state outer sphere inner coordination spheres of donor and acceptor complexes remain intact

Inner sphere mechanism

[Co(NH3)5Cl]2+ + [Cr(OH2)6]2+ [(NH3)5CoIII-Cl-CrII(OH2)5]4+ [(NH3)5CoII-Cl-CrIII(OH2)5]4+ [(NH3)5CoIII-Cl-CrII(OH2)5]4+ [(NH3)5CoII-Cl-CrIII(OH2)5]4+ [Cr(OH2)5Cl]3+ + [Co(OH2)6]2+ + 5NH3

Inner sphere mechanism

Substitution of Cl- on CrIII is too slow to occur on reaction timescale Sufficient conditions for inner sphere mechanism are: product must be substitutionally inert product must retain bridging ligand originally coordinated to the other reactant These put stringent requirements on choice of oxidant and reductant. Other methods do exist to verify inner vs outer sphere electron transfer

Outer sphere

Sufficient condition is that electron transfer is faster than ligand substitution on either metal Example is reduction of [RuBr(NH3)5]2+ by V2+ second order rate for electron transfer is 5.1 103 M-1 s-1 aquation rates for RuIII and VII are 1st 20 and 40 s-1

Marcus theory
1992 Nobel Prize for defining contributions to G Delineated the five steps leading from reactants to products

Five steps

Reactants diffuse together to form an outer sphere complex; both inner spheres are intact Bonds in complexes lengthen or shorten so that system begins to resemble the products Solvent shells reorganize to be more product-like Electron is transferred Products diffuse

Comments on mechanism
Equations are listed in text Work to bring reactants together is that associated with forming an outer sphere complex Franck-Condon principle states that electron transfer is much faster than nuclear motions, so nuclei are essentially in fixed positions during the course of electron transfer

Comments on mechanism

Solvent must also rearrange to accommodate the difference between reactants and products Solvent rearrangement depends on size and charge of reactants, solvent dielectric constants (static and optical) At transition state, wavefunctions describing reactants and products mix, yielding two energy states.

Comments on mechanism

See Figure 11.15 inner sphere reorganizational energy depends on differences in structure of reactants and products Strong interactions between reactant and product wavefunctions generate a large energy gap at transition state System stays on lower curve; probability of electron transfer at transition state is 1 Generally good agreement is observed (factor of 25 for well behaved systems)