Organometallic Approaches to Hydrocarbon Oxidation

这个无机、生物无机和有机金属化学项目的奖项支持加州理工学院化学系的John E. Bercaw博士对有机金属化合物氧化碳氢化合物的研究。希洛夫最初报道的含水铂卤化物将被研究。本工作的具体目标是探索希洛夫机制中C-H键激活步骤的机制，制备更多活性和稳健的与模型配合物相关的化合物，这些化合物已被证明可以影响C-H键的激活，制备一些含有氧化还原活性基团的衍生物，研究二氧与相关Pt（II）化合物的反应，并寻求将这些二氧反应偶联到希洛夫机制的方法。了解导致简单碳氢化合物羟基化的机理步骤将有助于确定希洛夫系统的局限性，并为如何使用双氧作为氧化剂实现碳氢化合物的催化羟基化提供见解。过渡金属化合物在化学工业中广泛用作催化剂。本项目重点开发C-H键快速选择性反应生成伯醇或其他部分氧化产物的催化剂。这样的反应有助于在后续的化工生产中直接使用烷烃原料。

This award in the Inorganic, Bioinorganic, and Organometallic Chemistry program supports research on hydrocarbon oxidation by organometallic compounds by Dr. John E. Bercaw of the Chemistry Department, California Institute of Technology. Aqueous platinum halides, originally reported by Shilov, will be studied. The specific goals of the work are to explore the mechanism of the C-H bond activation step in the Shilov mechanism, prepare more active and robust compounds related to model complexes that have been shown to effect C-H bond activation, prepare some derivatives containing redox active groups, examine the reactions of dioxygen with related Pt(II) compounds and seek ways to couple these dioxygen reactions to the Shilov mechanism. Understanding the mechanistic steps resulting in hydroxylation of simple hydrocarbons will help define the limitations of the Shilov system as well as provide insight into how to achieve catalytic hydroxylation of hydrocarbons using dioxygen as the oxidant. Transition metal compounds are used extensively as catalysts in the chemical industry. This project focuses on the development of catalysts for rapid and selective reaction of C-H bonds to form primary alcohols or other partially oxidized products. Such reactions could facilitate using alkane feedstocks directly in subsequent chemical production.