Metal-Oxo and Metal-Peroxo Intermediates in Oxidative Catalysis

无机化学、生物无机化学和金属有机化学项目的这一奖项支持普林斯顿大学的Jay Groves教授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的研究。该建议有四个重点领域：1)氧和过氧金属络合物之间的结构-反应性相关性；2)氧金属卟啉的脂肪族羟基化反应的动力学和机理，3)氧向卤化物离子的转移和水的氧化，以及4)铑卟啉介导的烯烃的反Markovnikov加氢官能化。我们将研究氧锰(V)卟啉体系的反常反应性，以便：1)通过观察周期关系来阐明反应中的电子效应，2)确定形成M=O-H键的强度，或者，等价地，M(IV)O-H的键离解能，3)确定为什么在相同的催化体系中，锰的行为与铁的行为如此不同4)确定定量自由能关系，推导结构与反应活性之间的关系，5)确定这些络合物是否能氧化卤离子和水。化学催化是国家和世界经济健康的核心，美国约30%的GNP和至少80%的化学工业依赖于催化过程。这项研究旨在发现几种类型的氧化催化的基本基础，并培训国家实现这些发现所提供的技术进步所需的人员，并为未来培训科学教师。

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.