Metal-Oxo and Metal-Peroxo Intermediates in Oxidative Catalysis

该奖项在无机、生物无机和有机金属化学项目中支持普林斯顿大学的杰伊·格罗夫斯教授的研究，以发现氧化催化的基本原理，并利用这些见解发明下一代催化剂。该提案有四个重点领域：1)氧和过氧金属配合物之间的结构-反应性相关性；2)氧金属卟啉对脂肪族羟基化反应的动力学和机理；3)氧转移到卤化物离子和水的氧化；4)铑卟啉介导烯烃反markovnikov加氢功能化反应。氧锰(V)卟啉体系的异常反应性将被研究，以便：1)通过观察周期关系阐明反应性中的电子效应，2)确定形成M=O- H键的强度，或者等价地，M(IV)O-H的键解离能，3)确定为什么在相同的配体体系中，在相同的催化体系中，锰与铁的行为如此不同，4)确定定量自由能关系并推断结构与反应性之间的关系。5)判断这些配合物是否能氧化卤化物离子和水。化学催化是国家和世界经济健康的核心，美国约30%的国民生产总值和至少80%的化学工业依赖于催化过程。这项研究的目的是发现多种氧化催化的基本基础，培养国家实现这些发现所带来的技术进步所必需的人才，培养未来的科学教师。

This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Professor Jay Groves of Princeton University to discover the basic principles of oxidative catalysis and to use these insights for the invention of the next generation of catalysts. The proposal has four focus areas: 1) structure-reactivity correlations among oxo- and peroxo-metal complexes; 2) kinetics and mechanism of aliphatic hydroxylation by oxometalloporphyrins, 3) oxygen transfer to halide ions and the oxidation of water, and 4) anti-Markovnikov hydrofunctionalization of olefins mediated by rhodium porphyrins.The unusual reactivity of oxomanganese(V) porphyrin systems will be investigated in order to: 1) Elucidate the electronic effects in reactivity by looking at periodic relationships, 2) Determine the strength of the forming M=O---H bond, or, equivalently, the bond dissociation energy of M(IV)O-H, 3) Determine why manganese behaves so much differently from iron with the same ligand system in the same catalytic regime, 4) Determine quantitative free energy relationships and deduce relationships between structure and reactivity, and 5) Determine whether these complexes can oxidize halide ions and water.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 oncatalytic processes. This research aims to discover the fundamental basis of a number of types of oxidative catalysis and to train the personnel that are necessary for the nation to achieve the technological advances offered by these discoveries and to train the teachers of science for the future.