Metal-Oxo and Metal-Peroxo Intermediates in Oxidative Catalysis

氧化催化中的金属-氧和金属-过氧中间体

• 批准号: 9814301
• 负责人: John Groves
• 金额: $ 63.3万
• 依托单位: Princeton University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1998
• 资助国家: 美国
• 起止时间: 1998-12-01 至 2002-11-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9814301&HistoricalAwards=false
• 关键词: Metal; Oxo; Peroxo; Intermediates; Oxidative

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.

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化学系的约翰·T·格罗夫斯博士对仿生氧化机制的研究。五种类型的反应将被研究：氧和过氧金属络合物的氧化；Ru卟啉的催化氧化；一氧化二氮的碳氢化合物的氧化；不对称氧化的催化剂；以及用于碳氢化合物氧化的非血红素二铁催化剂。这些反应的机理将使用快速动力学技术进行详细研究，包括快速混合方法、顺磁核磁共振松弛和同位素分馏。碳氢化合物的催化氧化在化工过程工业中仍然具有重要的基础意义和潜在的经济价值。了解潜在的机制有望导致重要的合成和工业有机化学的新方法，也将为重大的生化转变提供见解。开发一氧化二氮作为氧化剂将提供氧的工业生态替代品，因为它将利用尼龙生产的副产品产生的温室气体。