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.

该研究计划的目标是阐明金属催化原子转移反应的机制。 一般方法是表征所提出的催化循环中的反应性中间体，并分离催化中的基本步骤。 反应立体电子和配体设计用于探索对这些催化反应施加选择性的策略。 下一个赠款期的具体目标是：（1）继续阐述过氧和氧量复合物的化学； （2）设计和准备催化剂，用于现场选择性，形状选择性和对映选择性分子识别和催化氧合； （3）延长了在上一批赠款期间开发的金属氮化金属和金属酰亚胺化学因素，以激活和转移氮的催化剂。 其他物质与来自大气中的氧的大多数反应是由金属离子催化的，金属离子是蛋白质的成分，也可以作为水溶液的微量成分。 更好地理解金属催化的氧化反应的机制对于开发更有效的氧气催化剂非常重要，并更深入地了解某些重要酶的工作原理。 在上一个赠款期间，该研究小组合成了催化剂，这些催化剂非常有效地导致某些有机化学物质与氧气反应，以至于形成了几种可能产物中的一种，以及含有金属的化合物，这些化合物是催化生物氧化的某些酶的模型。