Intramolecular Electron Transfer at Metal Surfaces. I. Relative Energetics of Some Corresponding Outer- and Inner-Sphere Pathways Involving Halide and Pseudohalide Bridging Ligands

摘要

The electroreduction kinetics of a number of Co(III) ammine and ethylene-diamine complexes containing chloride, bromide, and isothiocyanate ligands have been studied at platinum- and gold-aqueous interfaces in order to investigate the consequences of attaching simple transition-metal reactants to electrocatalytic metal surfaces upon the electron-transfer energetics. The virtues of evaluating unimolecular rate constants k sub et (per sec) for comparing the energetics of electrochemical inner- and outer-sphere pathways are pointed out.