Theoretical Studies of Inorganic and Organometallic Systems

无机，生物无机和有机化学计划的这个奖项支持与Michael B博士的催化相关的理论研究。德州农工大学化学系大厅。 将研究与催化中的四个基本步骤有关的体系：氧化加成、取代、迁移插入和原子转移。 详细的C-H键活化的羰基铑配合物的早期阶段的动力学进行了研究。 将确定连接两个建议的溶剂化中间体的过渡态的性质和能量。 其他的研究将集中在铑催化的环化反应和钌催化的炔和烯烃二聚反应。 将模拟非经典二氢络合物和经典二氢络合物之间的转换。 将在模拟钼酶的模型系统中检查氧转移和插入。 计算结果将与已知的实验结果进行比较。 非局域密度泛函理论（DFT）和多组态自洽场（MCSCF）方法，特别是广义分子轨道方法（GMO 2），将用于稳定分子，反应中间体和过渡态的全梯度几何优化。 GMO 2方法非常适合过渡金属。 更高层次的方法将被用来确定势能面上的临界点。许多重要的工业反应的催化机理还不清楚。 在这项研究中，分子的电子状态及其反应途径的理论计算将被用来开发模型的反应，将与实验结果进行比较。 这可能有助于开发改进的催化剂。

This award in the Inorganic, Bioinorganic, and Organometallic Chemistry Program supports theoretical studies related to catalysis by Dr. Michael B. Hall of the Chemistry Department, Texas A&M University. Systems related to four fundamental steps in catalysis will be investigated: oxidative-addition, substitution, migratory-insertion, and atom transfer. Detailed kinetics of the early stages of C-H bond activation by a rhodium carbonyl complex will be studied. The nature and energy of the transition states connecting two proposed solvated intermediates will be determined. Other studies will concentrate on dirhodium catalyzed cyclizations and ruthenium catalyzed alkyne and alkene dimerizations. Transformations between non-classical dihydrogen complexes and classical hydrides will be modeled. Oxygen transfer and insertion will be examined in a model system that mimics molybdenum enzymes. Calculational results will be compared with known experimental results. Non-local density functional theory (DFT) and multiconfiguration self-consistent field (MCSCF) methods, especially generalized molecular orbital method (GMO2), will be used for full-gradient geometry optimization of stable molecules, reaction intermediates, and transition states. The GMO2 method is well-suited to transition metals. Higher level methods will be used to determine critical points on potential energy surfaces.Detailed mechanisms for catalysis of many important industrial reactions are not known. In this study, theoretical calculations of the electronic states of molecules and their reaction pathways will be used to develop models for reactivity that will be compared to experimental results. This could aid in the development of improved catalysts.