Reaction Design and Control of Comlex Electronic System. Tbeoretical Study

复杂电子系统的反应设计与控制。

• 批准号: 11166253
• 负责人: SAKAKI Shigeyoshi
• 金额: $ 29.7万
• 依托单位: Kumamoto 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-11166253/
• 关键词: electronic structure calculation; catalytic cycle; reaction mechanism; catalysis by metal complex; C-H bond activation; carbon dioxide fixation; complex electron system; transition metal complexes; 遷移金属錯体触媒; ヒトロシリル化反応; シラノン; メタセシス; σ結合活性化; 計算

1. Transition-metal catalyzed hydrosilylation of alkene, which is one of the typical catalytic reactions, was theoretically investigated with the DFT, MP2-MP4, and CCSD(T) methods. Theoretical calculations clearly indicate that when the platinum(0) complex is used as a catalyst this reaction proceeds through Chalk-Harrod mechanism which involves the insertion of alkene into the Pt-H bond, and that when the rhodium(I)) complex is used as a catalyst the reaction proceeds through: the modified Chalk-Harrod mechanism. The difference in the reaction mechanism arises from the numbers of d electron of platinum(II) and rhodium(III) complexes. Interestingly, the new reaction mechanism is theoretically proposed when Cp_2Zr(II) is used as a catalyst This new reaction mechanism involves the metathesis of Cp_2Zr(C_2H_4) with hydrosilane. This reaction mechanism is possible when the ヲミ-back donation from the metal center to ethylene is very strong..2. The C-H ヲメ-bond activation is one of the challen … More ging subject of recent research in theoretical and experimental field. In this work, we theoretically investigated heterolytic C-H ヲメ-bond activation of methane by palladium(II) and platinum(II) complexes, and found that driving force of this C-H activation is formation of strong O-H bond between the carboxylate ligand and the H of substrate. The palladium(II) complex is more useful for the C-H activation of benzene but the platinum(II) complex is more useful for the C-H activation of methane.3. Hydrogenation of carbon dioxide into formic acid catalyzed by the ruthenium(II) complex was theoretically investigated. From the calculations, it is clearly concluded that the reaction p through the insertion of carbon dioxide into the nrthenium(II)-hydride bond, isomerization ruthenium(II)-formate complex, and the a-bond metathesis of the ruthenium(II)-formate complex. The molecular dihydorgen. The metathesis takes place through the six-centered transition state completely different from the previous theoretical proposal. Less

1. 采用DFT、MP2-MP4和CCSD(T)方法对过渡金属催化烯烃硅氢化反应进行了理论研究。理论计算清楚地表明，当铂(0)配合物作为催化剂时，该反应通过粉笔-哈罗德机制进行，其中包括将烯烃插入到Pt-H键中；当铑(I)配合物作为催化剂时，该反应通过改进的粉笔-哈罗德机制进行。反应机理的不同是由铂（II）和铑（III）配合物的d电子数引起的。有趣的是，当Cp_2Zr（II）作为催化剂时，理论上提出了新的反应机理，该反应机理涉及Cp_2Zr（C_2H_4）与氢硅烷的复合反应。当从金属中心向乙烯的反给价很强时，这种反应机制是可能的。碳氢键活化是近年来理论界和实验界研究的热点问题之一。本文从理论上研究了钯（II）和铂（II）配合物对甲烷C-H - oh -键的异裂解活化，发现这种C-H活化的驱动力是羧酸配体与底物H之间形成强O-H键。钯（II）配合物对苯的碳氢活化更有用，而铂（II）配合物对甲烷的碳氢活化更有用。对钌（II）配合物催化二氧化碳加氢制甲酸进行了理论研究。从计算中可以清楚地得出，反应p通过二氧化碳插入到氮(II)-氢化键中，异构化钌(II)-甲酸配合物，以及a键复分解钌(II)-甲酸配合物。二氢分子。复合是通过六中心过渡态发生的，与以往的理论设想完全不同。少

项目成果

B.Biswas, M.Sugimoto, S.Sakaki: "C-H Bond Activation of Benzene and Methane by M(η^2-O_2CH)_2 (M=Pd or Pt). A Theoretical Study"Organometallics. Vol.19, No.19. 3895-3906 (2000)

B.Biswas、M.Sugimoto、S.Sakaki：“M(η^2-O_2CH)_2（M=Pd 或 Pt）对苯和甲烷的 C-H 键活化。理论研究”有机金属学，第 19 卷，第 1 期。 19. 3895-3906 (2000)

S. Sakaki, S. Kai, and M. Sugimoto: "Theoretical Study on ヲメ-Bond Activation of (HO)_2B-XH_3 (X=C, Si, Ge, or Sn ; M=Pd or Pt). Noteworthy Ccmtribution of the Boryl p_x-Orbital to M-Boryl Bonding and Activation of the B-X ヲメ-Bond"Organometallics. 18-23. 4

S. Sakaki、S. Kai 和 M. Sugimoto：“(HO)_2B-XH_3（X=C、Si、Ge 或 Sn；M=Pd 或 Pt）的 WOME 键活化的理论研究。值得注意的贡献硼基p_x-轨道与间-硼基键合以及B-X WOME-Bond”有机金属化合物的活化。18-23.4

S. Sakaki, T. Ohki, T. Takayama, M. Sugimoto, T. Kondo, and T. Mitsudo: "Participation of(ヲヌ3-llyi)ruthenhim(II) Coit^lexes in C-C Bond Formation and C-C Bond Cleavage. A Theoretical Study"Organometallics. 20-14. 3145-3158 (2001)

S. Sakaki、T. Ohki、T. Takayama、M. Sugimoto、T. Kondo 和 T. Mitsudo：“(wonu3-llyi)ruthenhim(II) Coit^lexes 在 C-C 键形成和 C-C 键裂解中的参与。A理论研究》有机金属学. 20-14. 3145-3158 (2001)

Y. Musashi and S. Sakaki: "Theoretical Study of Ruthenium-Catalyzed Hydrogenation of Carbon Dioxide into Formic Acid. Reaction Mechanism Involving a New Type of ヲメ-Bond Metathesis"J. Am. Chem. Soc.. 122-16. 3867-3877 (2000)

Y. Musashi 和 S. Sakaki：“钌催化二氧化碳氢化成甲酸的理论研究。涉及新型 Wome-Bond 复分解的反应机制”J. Am. 122-16。 3877 (2000)

S. Sakaki: "Frontier of Organic Compound Chemistry"Gakken. in press. 261

S. Sakaki：“有机化合物化学前沿”Gakken。