Metal-Oxo and Metal-Peroxo Intermediates in Oxidative Catalysis

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The Chemical Catalysis Program in the Chemistry Division at the National Science Foundation supports Professor John T. Groves of Princeton University for studies of oxidative catalysis. Hydrocarbon transformations will continue to play central roles in the global energy economy into the foreseeable future. Alkane oxygenations, water splitting reactions and the deoxygenation of carbon dioxide all can be envisioned to involve oxygen atom transfers. It is the central thesis of this program that recent conceptual advances in oxidative catalysis offer an unprecedented opportunity to develop abundant first-row transition metals as catalysts of these processes. The research will combine knowledge of the huge reservoir of hydrocarbon chemistry currently being practiced by aerobic and anaerobic organisms with insights derived from synthetic, biomimetic systems to find new catalysts. Broad application of this chemistry could have tremendous impact on the nation's and the world's chemical economy. The goal of this program is to understand and harness the breadth of high-valent transition metal chemistry involving metal oxo systems. Success in this endeavor could offer new methods of late-stage drug diversification and metabolite identification, new opportunities for energy transduction with hydrocarbons, new concepts for the development of fuel cells and new processes for disinfecting bioterrorism agents. The approach involves direct kinetic and spectroscopic methods to characterize reactive metal-oxo intermediates under conditions of active, fast catalysis. An important goal is to reveal the range of these new catalytic systems that employ recently-discovered entries into oxo- and dioxo-metal complexes, including new C-H halogenation protocols, with a focus on first-row transition metal based systems that have real prospects of being implemented on a massive scale.Discoveries from this research will help understand the basic principles of how chemical catalysis operates, and will use such insights to drive the invention of the next generation of catalysts and to train the personnel that are necessary for the nation to achieve technological advances in industry. Students and postdoctoral research associates from a variety of backgrounds and including underrepresented minority chemists as well as a number of undergraduates will be trained in the laboratory. Chemical catalysis is central to the economic health of the nation and the world with about 30% of the GNP of the United States and at least 80% of the chemical industry dependent upon catalytic processes. As a result the chemical industry is a major employer of US trained scientists. Human health is impacted by the selectivity of chemical and biochemical catalysis that is necessary for the pharmaceutical industry to produce new and pure drugs efficiently. Four patents have been filed over the past three years and a new company has been founded to commercialize advances from this and related projects, especially in the area of drug discovery. New technologies are also needed to allow the world economy to capture the vast resources of methane, for example, which are now largely wasted, and to give high value added to petroleum feedstock. New discoveries in oxidative catalysis in particular, which is the core activity of the proposed research described herein, are necessary to address these scientific, technological and environmental challenges.