Entropic and Enthalpic Contributions to the Solvent Dependence of the Thermodynamics of Transition-Metal Redox Couples. I. Couples Containing Aromatic Ligands

摘要

Variations in the solvent medium are generally expected to yield profound changes in the thermodynamics and kinetics of electron transfer reactions. The origins of the observed solvent effects are frequently manifold, arising from alterations in the chemical nature of the reacting species as well as the reactant-solvent interactions in both the ground reactant and transition states. We have embarked on a systematic study of solvent effects upon the electrode kinetics and thermodynamics of redox couples involving substitutionally inert cations where the oxidized and reduced species are both stable in the solution phase and differ only by one electron.