Catalytic Activation and Oxidation of C-H and C-C Bonds by Metal Species in Solution

森博士得到了无机化学、生物无机化学和金属有机化学计划的支持，研究均相催化剂的机理。他开发了一种以氯化铑为基础的催化系统，能够在氧气和一氧化碳存在的情况下将甲烷选择性氧化为甲醇或醋酸。此外，该体系将优先裂解高碳烷烃的碳-碳键，生成甲醇或醋酸。以氯化铜和钯为基础的第二个催化系统能够以与商业使用的工艺相当的速度氧化烷烃的碳-氢和碳-碳裂解产物。该研究所建议对双金属催化体系进行详细的动力学和机理研究。这项研究要解决的关键问题是一氧化碳和水在催化循环中的作用，以及碳-氢和碳-碳键对氧化产物的性质。具体的方法将包括动力学同位素效应研究和定制流动反应堆的设计和制造。选择性部分氧化化学是美国化学工业中探索最活跃的领域之一。将碳氢化合物转化为具有商业价值的原料，如醇和羧酸，具有重要的商业意义。由于该过程的增值性质，开发新的催化剂来执行这一功能具有重要的实际意义。

Dr. Sen is supported by the Inorganic, Bioinorganic and Organometallic Chemistry Program to study the mechanisms of homogeneous catalysts. He has developed a rhodium chloride based catalytic system that is capable of the selective oxidation of methane to methanol or acetic acid in the presence of oxygen and carbon monoxide. Further, this system will preferentially cleave carbon-carbon bond of higher alkanes to produce methanol or acetic acid. A second catalytic system based upon copper chloride and palladium is able to oxidize the carbon-hydrogen and carbon-carbon cleavage products of alkanes at rates comparable to commercially utilized processes. The PI has proposed to undertake a detailed kinetic and mechanistic study of the bimetallic catalytic system. Key issues to be addressed in this investigation are the roles of carbon monoxide and water in the catalytic cycle and the nature of carbon-hydrogen and carbon-carbon bonds upon oxidation products. Specific methodologies will include kinetic isotope effect studies and the design and fabrication of a custom flow reactor. Selective partial oxidation chemistry is one of the most actively explored fields in the US chemical industry. The conversion of hydrocarbons to commercially valuable feedstock materials such as alcohols and carboxylic acids is commercially important. The development of new catalysts to perform this function is of great practical importance due to the value-added nature of the process.