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

本研究计划的目的是阐明金属催化原子转移反应的机制。一般的方法是表征所提出的催化循环中的反应中间体，并分离催化的基本步骤。反应立体电子学和配体设计用于探索对这些催化反应施加选择性的策略。下一个资助期的具体目标是：(1)继续研究过氧金属和氧金属配合物的化学性质；(2)设计和制备位点选择性、形状选择性和对映选择性分子识别和催化氧化催化剂；(3)将之前资助期发展起来的金属氮化物和金属亚胺化学扩展到活化和转移氮的催化剂。其他物质与大气中的氧的大多数反应是由金属离子催化的，金属离子要么作为蛋白质的成分存在，要么作为水溶液的微量成分存在。更好地了解金属催化氧化反应的机理对于开发更有效的工业氧利用催化剂和更深入地了解一些重要酶的工作原理都是重要的。在之前的资助期间，这个研究小组已经合成了一些催化剂，这些催化剂非常有效地使一些有机化学物质与氧发生反应，这种反应只形成几种可能产物中的一种，还合成了一些含金属化合物，这些化合物是催化生物氧化的一些酶的模型。

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.