Structure-reactivity relationships in inorganic electrochemistry

Relationships between structure and electron transfer reactivity underlie many important electrochemical applications and provide fundamental insight to chemical and biological processes. The vast array of experimental techniques developed during the latter half of the twentieth century helped greatly to foster progress in this area, and the advent of powerful computational techniques such as density functional theory promises even more far-reaching developments. It is evident that molecular composition, geometric and electronic structure, and changes in these features influence the thermodynamics and kinetics of transition metal electron transfer reactions in predictable and understandable ways. Several examples drawn from the author's research program to illustrate this premise include the influence of sulfur versus oxygen donation on molybdenum-centered electron transfer, reactions in which a change in metal atom spin state accompanies electron transfer, and concomitant multi-electron transfer and metal-metal bond cleavage in binuclear, ligand-bridged complexes.