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

氧化催化中的金属氧化和金属过氧中间体（化学）

• 批准号: 8706310
• 负责人: John Groves
• 金额: $ 71.38万
• 依托单位: Princeton University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1987
• 资助国家: 美国
• 起止时间: 1987-04-15 至 1993-03-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=8706310&HistoricalAwards=false
• 关键词: Metal; Oxo; Peroxo; Intermediates; Oxidative

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.

本研究计划的目标是阐明 金属催化的原子转移反应 一般的做法是 表征拟定催化循环中的活性中间体， 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策略， 对这些催化反应施加选择性。 的具体目标 下一个赠款期是：（1）继续制定 过氧金属和氧代金属配合物化学;（2）设计和 制备催化剂，用于位点选择性、形状选择性和 对映选择性分子识别和催化氧化;以及 (3)以扩展金属氮化物和金属酰亚胺化学， 在前一个赠款期间开发的催化剂， 并转移氮气。 其他物质与大气中的氧气发生的大多数反应是 由金属离子催化，作为蛋白质成分存在， 作为水溶液的痕量成分。 更好地理解 金属催化氧化反应的机理是重要的， 用于开发更有效的工业催化剂 利用氧气，并更深入地了解一些 重要的酶起作用。 在上一个补助金期间， 研究小组已经合成了催化剂， 导致一些有机化学物质与氧气发生反应， 只形成几种可能的产品中的一种，以及金属- 含有某些酶的模型化合物， 生物氧化