Theoretical Studies of Inorganic and Organometallic Systems

无机和有机金属体系的理论研究

• 批准号: 9800184
• 负责人: Michael Hall
• 金额: $ 44万
• 依托单位: Texas A&M Research Foundation
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1998
• 资助国家: 美国
• 起止时间: 1998-06-15 至 2005-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9800184&HistoricalAwards=false
• 关键词: Theoretical; Studies; Inorganic; Organometallic; Systems

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.

该奖项在无机，生物促和有机金属化学计划中支持得克萨斯州农工大学化学系的迈克尔·B·霍尔（Michael B. Hall）博士有关的理论研究。 将研究与催化的四个基本步骤有关的系统：氧化剂，取代，迁移插入和原子转移。 将研究通过羰基复合物的C-H键激活的早期阶段的详细动力学。 将确定连接两个溶剂中间体的过渡状态的性质和能量。 其他研究将集中于dirhodium催化的环化和氟芬催化的炔烃和烯烃二聚化。 非古典二氢复合物与经典氢化物之间的转化将进行建模。 氧转移和插入将在模型系统中检查，该模型模拟钼酶。 计算结果将与已知的实验结果进行比较。 非局部密度功能理论（DFT）和多晶型自洽场（MCSCF）方法，尤其是广义分子轨道方法（GMO2），将用于稳定分子，反应中间体和过渡状态的全梯度几何优化。 GMO2方法非常适合过渡金属。 更高级别的方法将用于确定势能表面的关键点。用于催化许多重要工业反应的确定机制尚不清楚。 在这项研究中，分子电子状态及其反应途径的理论计算将用于开发反应性模型，以与实验结果进行比较。 这可能有助于发展催化剂的改善。