The Mechanism of Oxygen Atom Transfer

该项目涉及通过各种氧化剂（包括模拟单加氧酶（如P-450）的氧化剂）对饱和碳氢化合物羟基化的机制进行计算研究。以往工作的进一步发展将使计算化学承担氧化反应中O-O键裂解的能量学。不同反应途径之间的关系将以比较的方式进行研究，这将有望为二氧环、过氧亚硝酸和铁（III）氢过氧化物等反应提供一个全面的机制。单加氧酶模型利用卟啉铁（III）氢氧化物和过氧化氢配合物，使用多参比方法。有了这个奖项，有机和大分子化学项目继续支持特拉华大学Robert D. Bach教授的研究。巴赫教授使用计算机模拟化学反应，试图了解发生的事件的精确链。巴赫教授关注的一个重要反应是饱和碳氢化合物分子的氧化反应——由于几乎只存在强碳氢和碳碳单键，饱和碳氢化合物分子在大多数化学反应中是惰性的。这种反应是石油化工原料转化为有用的含氧物质（如醇）的一种方法。它也在生物体中由P-450酶进行。

This project involves the computational study of the mechanism of hydroxylation of saturated hydrocarbons by a variety of oxidants including those that model monooxygenases such as P-450. Further development of previous work will bring computational chemistry to bear on the energetics of O-O bond cleavage during oxidation reactions. The relationships between different reaction pathways will be examined in a comparative manner that will hopefully provide an all encompassing mechanism for such reactions as dioxirane, peroxynitrous acid, and iron (III) hydroperoxides. Monooxygenase models utilize porphyrin iron(III) hydroxides and hydrogen peroxide complexes, using multireference methods.With this Award, the Organic and Macromolecular Chemistry Program continues support for the research of Professor Robert D. Bach of the University of Delaware. Professor Bach uses computers to model chemical reactions in an attempt to learn the precise chain of events that occur. An important reaction and one that Professor Bach focuses on is the oxygenation of saturated hydrocarbon molecules -- those that are inert to most chemical reactions due to almost exclusive presence of strong C-H and C-C single bonds. This kind of reaction is one way in which petrochemical feedstocks are converted into useful oxygen-containing materials such as alcohols. It also is carried out in living organisms by the P-450 enzyme.