The Role of Reactant Vibrational Excitation in Transition Metal Chemistry

在这个由化学部实验物理化学计划资助的项目中，Davis将研究反应物振动能在涉及基态中性过渡金属原子和小的不饱和过渡金属络合物的碳-氢和碳-碳键活化反应中的作用。将使用直接红外振动激发或受激拉曼泵浦(SRP)来选择性地制备反应物。将研究双分子和单分子反应。将使用交叉分子束和157 nm紫外光电离中性反应产物来确定角和速度分布。振动泛音诱导挥发性过渡金属单体和二元络合物的单分子分解将被研究。过渡金属中心促进的通常不反应的碳氢键的化学变化在工业催化过程以及有机和有机金属合成中具有重要意义。本项目所做的研究将为应用于键活化反应的最先进的理论和动力学方法的测试提供重要的基准信息。研究生和本科生将参与这项研究。他们将为在学术界、工业界或政府实验室深造或就业做好准备。

In this project, funded by the Experimental Physical Chemistry Program of the Chemistry Division, Davis will investigate the role of reactant vibrational energy in carbon-hydrogen and carbon-carbon bond activation reactions involving ground state neutral transition metal atoms and small unsaturated transition metal complexes. Direct infrared vibrational excitation or stimulated Raman pumping (SRP) for state-selective preparation of reactants will be employed. Bimolecular and unimolecular reactions will be studied. Angular and velocity distributions will be determined using crossed molecular beams and 157 nm ultraviolet radiation to photoionize neutral reaction products. Vibrational overtone induced unimolecular decomposition of volatile transition metal monomer, as well as binary complexes will be investigated. Chemical changes in normally unreactive hydrocarbon bonds facilitated by transition metal centers is of great importance in industrial catalytic processes and in organic and organometallic synthesis. The research done in this project will provide important benchmark information for tests of state-of-the-art theoretical and dynamic methods applied to bond activation reactions. Graduate and undergraduate students will participate in this research. They will be prepared for advanced studies or employment in academia, industry, or government laboratories.