Metal-Oxo and Metal-Peroxo Intermediates in Oxidative Catalysis (Chemistry)

点击翻译按钮获取中文摘要

The goals of this research program are to elucidate the mechanisms of metal-catalyzed atom transfer reactions. The general approach is to characterize reactive intermediates in proposed catalytic cycles and to isolate the elementary steps in catalysis. Reaction stereoelectronics and ligand design are used to explore strategies to impose selectivity on these catalytic reactions. Specific goals for the next grant period are: (1) to continue the elaboration of the chemistry of peroxometal and oxometal complexes; (2) to design and prepare catalysts for site-selective, shape-selective and enantioselective molecular recognition and catalytic oxygenation; and (3) to extend the metal nitride and metal imide chemistry which was developed in the previous grant period toward catalysts which activate and transfer nitrogen. Most reactions of other substances with oxygen from the atmosphere are catalyzed by metal ions, present either as constituents of proteins or as trace constituents of water solutions. Better understanding of the mechanisms of metal-catalyzed oxidation reactions is important both for the development of more efficient catalysts for industrial utilization of oxygen and for a deeper understanding of how some important enzymes work. During the previous grant period this research group has synthesized catalysts which are very efficient in causing some organic chemicals to react with oxygen in such a way that only one of several possible products are formed, as well as metal- containing compounds which are models of some enzymes that catalyze biological oxidations.