Dr. David Stanbury, Department of Chemistry, Auburn University, is supported by the Inorganic, Bioinorganic and Organometallic Chemistry Program of the Chemistry Division for research into kinetics and mechanisms of reactions of main group radicals. A series of four research projects will be undertaken. The first will be on the reactions of iodide with one-electron outer-sphere transition-metal oxidants in nonaqueous solutions. Interest in these reactions arises from their relevance to photoelectrochemical cells, where oxidation of iodide in nonaqueous media by related oxidants is an essential component of their design. The second focuses on reactions of the thiols cysteine and glutathione in aqueous media with classical outer-sphere transition-metal oxidants. In this case the motivation is the relevance of the work to biochemistry, since these two thiols are the primary redox-active sulfur compounds in living organisms. The third is an investigation of the oxidation of hydroxylamine by classic outer-sphere oxidants in aqueous media. This reaction poses a conundrum, because simple electron-transfer oxidation is ruled out by thermochemical considerations; a hydrogen-atom-transfer mechanism is suggested, which is quite unusual among reactions of main-group species in aqueous solution. The fourth is a study of the aqueous oxidation of nitric oxide with chlorite. Here, electron transfer seems to be quite unlikely, and a variety of atom-transfer mechanisms are suggested; the reaction has not been studied before, but it is crucial to the operation of flue gas scrubbers in the petrochemical industry.
In this project new classes of reactivity will be uncovered. As mentioned above, the iodide project will contribute to developing solar energy technology. The thiol project will contribute to the understanding of general sulfur metabolism. The hydroxylamine project will contribute to an understanding of biological nitrification. The nitric oxide/chlorate project will aid in the development of improved technologies for abatement of pollution by nitrogen oxides. The projects will strengthen the scientific infrastructure of society through the advanced training and education of undergraduate, graduate, and postdoctoral students.
