This project, supported in the Analytical and Surface Chemistry Program, focusses on fundamental investigations of the electron transfer chemistry of organometallic compounds of interest as representative reaction intermediates in catalytic processes. During the tenure of this three-year continuing grant, Professor Geiger and his students at the University of Vermont will study the effects of structure on the electrochemical reactivity of organometallic compounds containing 17 and 19 valence electrons (17e, 19e). Using a broad suite of electrochemical and spectroscopic probes of structure and dynamics, the Vermont investigators will explore the fundamental chemistry of these systems. Additionally, they will develop new, fiber optic based infrared and near-infrared spectroelectrochemical techniques and apply them to these studies. This fundamental research addresses questions of how the structure of organometallic compounds, particularly those of cobalt and rhodium containing 17 and 19 valence electrons, affects their electron transfer properties. These questions are important to a greater understanding of the basic chemistry of these systems and the potential utility of this class of compounds in analytical sensors, photooptical devices, conducting polymers, and electrocatalysis. Additionally, this research facilitates the development of new spectroelectrochemical probes for the study of interfacial electron transfer that are expected to find broad application.