Elementary Kinetics of Pulsed Laser Initiated OrganometallicReactions in the Gas Phase

在无机化学、生物无机化学和金属有机化学项目的这一奖项中，普渡大学的爱德华·R·格兰特将继续和扩大他目前对气相有机金属化合物化学的研究。这项工作的目的是表征这些分子在气相中的重要基元反应的动力学和能量学。脉冲激光辐射将被用来启动反应。瞬时红外和核磁共振光谱检测方法跨越了从纳秒到几个小时的时间范围，将用于监测反应的进展。对这些基本反应过程的了解也将有助于催化科学和潜在有用催化剂的开发。要研究的类型反应包括：(1)有机金属化合物与两个电子配体的基本解离和复合反应，包括不饱和碳氢化合物和一氧化碳，(2)不饱和金属中心与Sigma-(H-H)和(C-H)键的双配位相互作用，(3)金属-氧配合物的气相转变，(3)金属-氧配合物的气相转变，(2)不饱和金属中心与Sigma-(H-H)键和(C-H)键的双配位相互作用。(4)早期过渡金属电致碳氢活化反应。

In this award in the Inorganic, Bioinorganic and Organometallic Chemistry Program, Edward R. Grant of Purdue University will extend and expand his current investigations on the chemistry of gas phase organometallic compounds. The purpose of the work is to characterize the kinetics and energetics of important elementary reactions of these molecules in the gas phase. Pulsed laser radiation will be used to initiate the reactions. Transient infrared and nuclear magnetic resonance spectroscopic detection methods that span the range of time scales from nanoseconds to hours, will be used to monitor the progress of the reactions. The understanding of these elementary reaction processes will also contribute to the science of catalysis and to the development of potentially useful catalysts. The type reactions to be studied include: (1) elementary dis- sociation and recombination reactions of organometallic com- pounds with two electron ligands, including unsaturated hydrocarbons and carbon momoxide; (2) two-coordinate inter- actions of unsaturated metal centers with sigma-(H-H) and (C-H) bonds; (3) gas phase transformations of metal-oxo complexes; and (4) early transition metal electroplilic carbon-hydrogen activation reactions.