Dynamic Solvent Effects in Alcohol Solutions for Electron Transfer Reactions Involving the Metallocenes.

摘要

Kinetic data for simple electron transfer reactions, both homogeneous and heterogeneous, are examined for ferrocene, cobaltocene and other metallocenes in both aprotic and protic alcoholic solvents. Attention is focussed on the solvent dynamical effect for the pre-exponential factor of the electron transfer rate constant. It is shown that this effect, which has heretofore been considered anomalous in the alcohols, can be understood on the basis of the parameters for the second dielectric relaxation process, that is, by assuming that the reactant and product are chiefly solvated by solvent monomers, not by hydrogen bonded clusters.