Dr. Edwin S. Gould, Chemistry Department, Kent State University, is supported in the Inorganic, Bioinorganic, and Organometallic Chemistry Program, for investigations of aqueous phase oxidation-reduction reactions which emphasize less common oxidation states. Two areas will be studied: 1) reductions with unipositive indium and 2) metal ion catalysis of oxidations by peroxynitrite. In the first part of the study the factors that determine when In(I) reacts by 1e and when it reacts by 2e pathways will be defined. These data then will be used to determine which ligating units will allow effective inner-sphere bridging in indium (I) reactions and to learn how the reactivity of In(I) compares with that of other 2e oxo-acceptor species. In the second part of the project, the ability of transition metal catalysts to modify rates of the reactions of the peroxynitrite ion will be evaluated. In particular, conversions with both one and two electron reductants will be studied and problems associated with maintaining effective concentrations of catalytic metal centers in the high pH region necessary for the survival of peroxynitrite will be addressed. Reactions in which electrons are transferred between reactants are of enormous importance in virtually all areas of pure and applied chemistry. In this project the little studied indium +1 ion will be studied in order to develop fundamental knowledge about its ability to provide one and two electrons to chemical processes. This will provide background information to facilitate the develoment of further applications for this species. The peroxynitrite ion, the subject of the second part, is a powerful oxidant and is formed in biological systems by the coupling of nitric oxide and superoxide. Transformations of this ion with reductants are complicated by the decomposition of peroxynitrite to nitrate and this study will develop the behavior of this biologically ubiquitous and unusually reactive peroxo species. In addition to the chemical studies, an important goal of this project is the training of a cadre of chemists with a strong background in inorganic solution chemistry. This is an area of great importance, but one in which there are few young practitioners.
