Theoretical Studies of Structure and Reactions of Transition Metal Atoms, Ions, Complexes and Clusters

过渡金属原子、离子、配合物和团簇的结构和反应的理论研究

• 批准号: 0209660
• 负责人: Keiji Morokuma
• 金额: $ 34.5万
• 依托单位: Emory University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2002
• 资助国家: 美国
• 起止时间: 2002-07-15 至 2006-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0209660&HistoricalAwards=false
• 关键词: Theoretical; Studies; Structure; Reactions; Transition

Keiji Morukuma of Emory University is supported by the Theoretical and Computational Chemistry Program to study the structure and reactions of transition metal clusters and complexes using ab initio, density functional, and ONIOM (hybrid molecular orbital plus molecular orbital or molecular mechanics) methods. The ONIOM method, which allows inclusion of complex real ligands into computations, will be developed and calibrated for large transition metal complexes. As well, the ONIOM-PCM (polarized continuum model) method will be tested and employed to study organometallic reactions in solutions. Close contact with experimental chemists will be maintained, while experimentally relevant problems are explored. Gas phase reactions of dihydrogen, alkynes, and alkenes with bare transition metal clusters and C-C, C-H and molecular nitrogen bond activation, along with skeletal rearrangement, on trinuclear ruthenium complexes will be studied, with the goal of examining metal clusters that can catalyze reactions not possible on a single transition metal center. As well, the mechanisms of several important reactions in organometallic chemistry will be elucidated, encompassing a wide variety of reactions of mononuclear transition metal complexes and full homogeneous catalytic cycles including (a) olefin copolymerization, (b) element-element addition to unsaturated hydrocarbons, (c) utilization of metal-ligand multiple bonds, (d) transition metal catalyzed cycloisomerizations, (e) reaction of allylic compounds with formic acid or metal-hydride, and olefin metathesis. The knowledge of structure, spectroscopic properties, and energies of reaction intermediates and transition states that will be gained from this research is expected to promote fundamental understanding as well as aid logical design of new catalysts for better control of complicated chemical reactions. This computational research project complements efforts in experimental chemistry, and is expected to promote the fundamental understanding of complex chemical reactions. Although many industrial catalytic processes have been developed in the past, the chemical industry is trying hard to switch to catalysts using clean homogeneous processes. Designing efficient catalysts is one of the areas where computational chemistry can make a substantial impact in the chemical industry.

埃默里大学的Keiji Morukuma由理论和计算化学计划支持，使用从头算，密度泛函和ONIOM（杂化分子轨道加分子轨道或分子力学）方法研究过渡金属簇合物和络合物的结构和反应。 ONIOM方法，它允许复杂的真实的配体纳入计算，将开发和校准大型过渡金属络合物。 此外，ONIOM-PCM（极化连续模型）方法将被测试和用于研究溶液中的有机金属反应。 将保持与实验化学家的密切联系，同时探索实验相关的问题。 研究了二氢、炔和烯烃与裸过渡金属簇的气相反应，以及C-C、C-H和分子氮键的活化，沿着骨架重排，在三核钌配合物上的反应，目的是考察可以催化在单个过渡金属中心上不可能的反应的金属簇。 此外，还将阐明有机金属化学中几个重要反应的机理，包括单核过渡金属配合物的各种反应和全均相催化循环，包括（a）烯烃共聚，（B）元素-元素加成到不饱和烃，（c）金属-配体多重键的利用，（d）过渡金属催化的环异构化，（e）烯丙基化合物与甲酸或金属氢化物的反应，以及烯烃复分解。从本研究中获得的反应中间体和过渡态的结构，光谱性质和能量的知识，预计将促进基本的理解，以及援助新的催化剂的逻辑设计，以更好地控制复杂的化学反应。 这个计算研究项目补充了实验化学的努力，并有望促进对复杂化学反应的基本理解。 尽管过去已经开发了许多工业催化过程，但化学工业正在努力切换到使用清洁均相过程的催化剂。 设计高效催化剂是计算化学可以在化学工业中产生重大影响的领域之一。