The Mechanism of Oxygen Atom Transfer

该项目涉及各种氧化剂对饱和烃的羟基化机理的计算研究，包括那些模拟单加氧酶如P-450的氧化剂。 以前的工作的进一步发展将带来计算化学承担在氧化反应过程中的O-O键断裂的能量学。 不同的反应途径之间的关系将进行检查，在比较的方式，这将有望提供一个全面的机制，如二环氧乙烷，过氧亚硝酸，和铁（III）氢过氧化物等反应。 单加氧酶模型利用卟啉铁（III）氢氧化物和过氧化氢复合物，使用多参考方法。特拉华州大学的巴赫。 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。 一个重要的反应，也是巴赫教授重点关注的反应是饱和烃分子的氧化--由于几乎完全存在强C-H和C-C单键，这些分子对大多数化学反应是惰性的。 这种反应是将石化原料转化为有用的含氧材料如醇的一种方式。 在生物体中，它也通过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.