Metal-Oxo and Metal-Peroxo Intermediates in Oxidative Catalysis

无机，生物无机和有机化学计划的这一奖项支持普林斯顿大学的Jay格罗夫斯教授的研究，以发现氧化催化的基本原理，并将这些见解用于下一代催化剂的发明。 该计划有四个重点领域：1）氧代和过氧金属配合物之间的结构-反应性相关性; 2）氧代锰卟啉催化的脂肪族羟基化反应的动力学和机理; 3）氧向卤离子的转移和水的氧化; 4）铑卟啉介导的烯烃的反马尔可夫氢官能化。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，确定M（IV）O-H的键离解能，3）确定为什么锰在相同的催化体系中与具有相同配体系统的铁的行为如此不同，4）确定定量的自由能关系并推导结构与反应性之间的关系，和5）确定这些复合物是否可以氧化卤素离子和水。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一些类型的氧化催化的基本基础，并培养必要的人员，为国家实现这些发现所提供的技术进步，并为未来培养科学教师。

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.