Molecular Electron Transfer

This chapter summarizes the observations on electron transfer reactions of transition metal complexes. Bimolecular, outer-sphere, self-exchange electron transfer reactions conform reasonably well to the classical theory that their rate differences are largely a function of their differences in nuclear reorganizational energies. However, some allowance for electronic contributions is necessary. A range of covalently linked electron transfer systems is surveyed and the reorganizational energy contributions are diminished in most of them relative to their outer-sphere analogs. Donor/acceptor electronic mixing, including that of the linker, accounts for many of the physical properties of the linked systems. Extensions to more extended systems are considered.