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: 9627775
• 负责人: Keiji Morokuma
• 金额: $ 38.38万
• 依托单位: Emory University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1996
• 资助国家: 美国
• 起止时间: 1996-07-01 至 2001-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9627775&HistoricalAwards=false
• 关键词: Theoretical; Studies; Structure; Reactions; Transition

The Theoretical and Computational Chemistry Program is supporting Prof. Keiji Morokuma at Emory University in his theoretical research on transition metals and their complexes. High level ab initio theoretical calculations are applied to a wide range of problems on structure and reactions of transition metal atoms, ions, complexes and clusters. The potential energy surfaces of a variety of chemical reactions will be calculated, ranging from gas phase reactions of bare transition metal ions and atoms and simple complexes, activation of various bonds by complicated transition metal complexes, the potential energy profiles of full catalytic cycles by organometallic catalysts, and reactions of transition metal clusters and cluster complexes. In addition to the standard ab initio molecular orbital (MO) methods, the Integrated Molecular Orbital + Molecular Mechanics (IMOMM) method and the integrated MO + MO (IMOMO) method, developed recently by the principle investigator, will be used for studies of reactions involving complicated ligands. Theoretical studies of full catalytic cycles by transition metal complexes, which still remain a challenge to theoreticians, will be performed for (1) boration of alkenes and alkynes by Pt(0) and Pd(0) complexes, (2) regio- and enantio-selective hydroformylation of olefins by Rh(I) catalyst with a chiral ligand BINAPHOS, and (3) Murai's C-H activation of aromatic ketones by Ru complexes. In addition copolymerization of olefin and CO catalyzed by Pd(II) complex and dehydrogenative polymerization of silanes by zirconocene catalysts will be studied. In the boration of alkenes and alkynes, Pd(0) and Pt(0) have very different reactivities to different B-X bonds, and the origin of the difference will be studied. In enantioselective hydroformylation, the different selectivity with different phosphine ligands will be studied with the IMOMM method to provide a clue for design of better ligands. The knowledge to be obtained through this research, such as structure, spectroscopic properties and energies of reaction intermediates and transition states, is complementary to that gained from experiments, and is expected not only to promote the fundamental understanding of complicated chemical reactions of transition metal complexes but also to help logical design of new catalysts for better control of complicated chemical reactions. Close contact with experimental groups will be maintained throughout the proposed research.

理论和计算化学计划是支持教授。 Emory大学的Keiji Morokuma在他的理论研究中， 过渡金属及其配合物。高级从头算理论 计算适用于广泛的结构问题， 过渡金属原子、离子、络合物和簇合物的反应。的 各种化学反应的势能面将是 计算，范围从裸过渡金属的气相反应 离子和原子以及简单的络合物，通过 复杂的过渡金属配合物，势能曲线， 通过有机金属催化剂的全催化循环，以及 过渡金属簇合物和簇合物。除了有 标准从头算分子轨道（MO）方法，积分 分子轨道+分子力学（IMOMM）方法和集成 MO + MO（IMOMO）方法，最近由主要研究者开发， 将用于研究涉及复杂配体的反应。 过渡金属全催化循环的理论研究 复合物，仍然是理论家的挑战，将是 用于（1）通过Pt（0）和Pd（0）的烯烃和炔烃的硼化 配合物，（2）Rh（I）催化剂与手性配体的区域选择性和对映选择性烯烃加氢反应 BINAPHOS和（3）Murai的Ru对芳香酮的C-H活化 配合物此外，还研究了烯烃与CO的共聚合反应， Pd（II）络合物和硅烷的分解聚合 将研究二茂锆催化剂。在烯烃的硼化反应中， 炔，Pd（0）和Pt（0）对不同的炔具有非常不同的反应性。 B-X键，并将研究差异的起源。在 对映选择性加氢，不同的选择性与 将用IMOMM方法研究不同的膦配体， 为设计更好的配体提供了线索。 通过本研究获得的知识，如反应中间体的结构，光谱性质和能量， 过渡态，是从实验中得到的补充，并预计 不仅促进了对复杂化学的基本理解， 反应的过渡金属配合物，而且还有助于逻辑设计 新催化剂的开发，以更好地控制复杂的化学反应。 在整个过程中，将与实验组保持密切联系。 提议的研究。