Theoretical Studies on Controlling of Chemical Reactions Catalyzod by Transidon Metal Complexes

Transidon金属配合物催化化学反应控制的理论研究

• 批准号: 11166226
• 负责人: KOGA Nobuaki
• 金额: $ 7.3万
• 依托单位: Nagoya University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas (A)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11166226/
• 关键词: transition metal complex catalyst; MO calcutations; DFT calculations; electrostatic potential; CH bond activation; migration reaction; alkyne hydration; electronegativity; 遷移金属錯体; 置換基効果; アルカンのカルボニル化; 触媒サイクル; 錯体触媒; ベンゾイミダゾール; ポテンシャルエネルギー面; 遷

Transition states as well as reactive intermediates play important roles in catalytic reactions, and it is essential in understanding such reactions and designing new reactions to know the geometrical and electronic structures of these transient species. Accordingly, we have theoretically investigated the reaction mechanism and die factors controlling diem by using die hybrid density functional theory and ab initio molecular orbital method. The subjects covered are 1) highty ortho selective addition of aromatic CH bond to olefin catalyzed by Ru(H)_2(COXPR_3)_2 complex, 2) structure and reactivity of (substituted arene)Cr(CO)_3 complexes, 3) anti-Markovnikov regiochemistry in ruthenium-catalyzed hydration of 1 - Alkynes, 4) CO insertion into Pd-carbon bond on Pd-Co heterodinuclear complex, 5) CH bond activation of benzimidazole by trinuclear Ru complex, 6) electronic effect of substituted phosphine ligands, 7) atomic and group electronegativities, and 8) a consistent approach toward atomic radii.

过渡态和活性中间体在催化反应中起着重要的作用，了解这些过渡态的几何结构和电子结构对于理解这些反应和设计新的反应是至关重要的。在此基础上，我们利用杂化密度泛函理论和从头算分子轨道方法，对反应机理和影响因素进行了理论研究。本文研究了Ru（H）_2（COXPR_3）_2配合物催化的芳香CH键与烯烃的高邻位选择性加成反应;（取代芳烃）Cr（CO）_3配合物; 3）钯催化1 -炔水合反应中的反马氏区域化学; 4）CO插入Pd-Co异双核配合物上的Pd-碳键; 5）三核钌配合物对苯并咪唑的CH键活化; 6）取代膦配体的电子效应; 7）原子和基团的电负性; 8）原子半径的一致性。

项目成果

A.Fukuoka: "Enhancement of CO Insertion into Pd-Carbon Bond on Pd-Co Heterodinuclear Complex"Organometallics. (in press).

A.Fukuoka：“增强 CO 插入 Pd-Co 异双核配合物上的 Pd-碳键”有机金属。

T. Matsubara: "Density Functional Study on Highly Ortho Slective Addition of Aromatic CH Bond to Olefin Catalyzed by Ru(H)_2(CO)(PR_3)_2 Complex"Organometallics. (in press).

T. Matsubara：“Ru(H)_2(CO)(PR_3)_2 配合物催化芳香族 CH 键与烯烃高度邻位选择性加成的密度泛函研究”有机金属化合物。

A.Fukuoka: "Enhancement of CO Insertion into Pd-Carbon Bond on Pd-Co Heterodinuclear Complex"Organometallics. 20. 2065-2075 (2001)

A.Fukuoka：“增强 CO 插入 Pd-Co 异双核配合物上的 Pd-碳键”有机金属。

C.H.Suresh: "A Molecular Electrostatic Potential Bond Critical Point Model for Atomic and Group Electronegativities"J. Am. Chem. Soc.. 124. 1790-1797 (2002)

C.H.Suresh：“原子和基团电负性的分子静电势键临界点模型”J。

Tokunaga, M.: "Ruthenium-Catalyzed Hydration of 1-Alkynes to Give Aldehydes : The Mechanism of anti-Markovnikov Regiochemistry"J. Am. Chem. Soc.. 123. 11917-11924 (2001)

Tokunaga, M.：“钌催化 1-炔烃水合生成醛：反马尔可夫尼科夫区域化学的机制”J.