This award in the Inorganic, Bioinorganic, and Organometallic Chemistry Program provides continuing support to research on the mechanism of oxidation reactions of organometallic compounds by Dr. James M. Mayer of the Chemistry Department, University of Washington. The formation of carbon-oxygen bonds using a metal-oxo group as the oxygen source is the focus of the investigation. The migration of aryl and alkyl groups from a metal center to an oxo group--an important step in the reaction mechanism--will be explored in detail. A variety of reactions involving intra- and inter- molecular nucleophilic attack at oxo groups will be studied. The rhenium-oxo-hydridotris(pyrazolyl)borate system will be used to generate, isolate, and study migrations involving electrophilic oxo groups. The oxidizing rhenium(VII) compounds are formed by oxygen atom transfer to stable rhenium(V) compounds. Other studies will explore the range of these reactions, including alkyl, alkene, arene, and thioether oxidations. Oxidation is an important commercial process in applications ranging from pharmaceutical synthesis to waste treatment, but the ability to control oxidation reactions is limited. This project addresses fundamental issues concerning mechanisms of oxidation of organic substances and will have impact on the ability to control organic oxidations. .
