The Mechanism of Oxygen Atom Transfer

有机动力学项目的这笔赠款支持韦恩州立大学罗伯特·D·巴赫教授的工作，他用高水平从头算方法研究了烷基过氧化物、金属氢氧化物、过氧酸、二氧六环和羰基氧化物的结构和反应活性。具体地说，将分析氧原子从过氧甲酸、二氧六环、一氧化碳、过氧化氢和过氧钒到乙烯和其他分子(如氨、膦和硫化物)的转移。重点讨论了溶剂和取代基对这些转变的影响，以及它们对双自由基态和异构化的影响。这项研究将讨论夏普莱斯的环氧化反应。在这个项目中，罗伯特·巴赫博士将进行计算研究，以解决氧化反应的基本方面。他的高水平从头算方法旨在深入了解烷基过氧物、金属羟基过氧物、过氧酸、二氧六环和羰基氧化物的结构、电子性质和溶剂对氧原子转移反应的影响。这些研究旨在促进对金属催化氧化的理解，金属催化氧化在工业、有机合成和生物化学中普遍存在，并可能导致更多的环境友好过程。

This grant from the Organic Dynamics Program supports the work of Professor Robert D. Bach at Wayne State University to study the structures and reactivities of alkyl peroxides, metal hydroperoxides, peroxy acids, dioxiranes, and carbonyl oxides by high level ab initio methods. Specifically, the oxygen atom transfer from peroxyformic acid, dioxirane, carbonyl oxide, peroxide, and vanadium peracid to ethylene and other molecules like ammonia, phosphine, and sulfides will be analyzed. Emphasis is given to the solvent and substituent effects on these transitions and their influence on the biradical states and isomerizations. The study will address the Sharpless epoxidation. %%% In this project Dr. Robert Bach will conduct computational studies to address fundamental aspects on oxidation reactions. His high level ab initio approach aims to provide insight into the structures, electronic properties, and solvent effects on the oxygen atom transfer reactivities of alkyl peroxides, metal hydroxyperoxides, peroxyacids, dioxiranes, and carbonyl oxides. These studies aim to advance the understanding of metal catalyzed oxidations that are ubiquitous in industry, organic synthesis, and biochemistry and may lead to more environmental benign processes.