Metal-Oxo and Metal-Peroxo Intermediates in Oxidative Catalysis

该无机、生物无机和有机金属化学项目奖项支持普林斯顿大学化学系的 John T. Groves 博士对仿生氧化机制的研究。 将研究五种类型的反应： 含氧和过氧金属络合物的氧化；钌卟啉催化氧化；通过一氧化二氮进行烃氧化；不对称氧化催化剂；和用于碳氢化合物氧化的非血红素双铁催化剂。 将使用快速动力学技术详细研究这些反应的机理，包括快速混合方法、顺磁核磁共振弛豫和同位素分馏。碳氢化合物的催化氧化仍然是化学加工工业中的根本利益和潜在的巨大经济价值。 了解潜在的机制有望为重要的合成和工业有机化学带来新的方法，并为重要的生化转化提供见解。 开发一氧化二氮作为氧化剂将提供氧气的工业生态替代品，因为它将利用尼龙生产副产品产生的温室气体。

This award in the Inorganic, Bioinorganic, and Organometallic Chemistry Program supports research on biomimetic oxidation mechanisms by Dr. John T. Groves of the Chemistry Department, Princeton University. Five types of reactions will be investigated: oxidations by oxo- and peroxo-metal complexes; catalytic oxidation by ruthenium porphyrins; hydrocarbon oxygenation by nitrous oxide; catalysts for asymmetric oxygenation; and non-heme di-iron catalysts for oxidation of hydrocarbons. The mechanisms of these reactions will be studied in detail using fast kinetic techniques, including rapid-mixing methods, paramagnetic NMR relaxation, and isotopic fractionation.Catalytic oxygenation of hydrocarbons continues to be of fundamental interest and potentially of great economic value in the chemical process industry. Understanding the underlying mechanisms is expected to lead to new approaches to important synthetic and industrial organic chemistry, and also to offer insights into significant biochemical transformations. Development of nitrous oxide as an oxidant would offer an industrially ecological alternative to oxygen since it would utilize a greenhouse gas generated as a byproduct of nylon production.