Design of Reaction Metal Sites toward Unique Activation of Small Molecules

反应金属位点设计以实现小分子的独特活化

• 批准号: 09102004
• 负责人: HIDAI Masanobu
• 金额: $ 128.64万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Specially Promoted Research
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09102004/
• 关键词: dinitrogen complex; ammonia; molybdenum; tungsten; sulfur; polynuclear complex; chalcogenide cluster; catalytic reaction; ピロール

The present study revealed that the cationic ruthenitum dihydrogen complexes trans-[RuCl (H_2)(diphosphine)_2]^+ derived from the coordinatively unsaturated ruthenium complexes and dihydrogen react with the tungsten dinitrogen complex cis-[W (N_2)_2 (PMe_2Ph)_4] to afford ammonia under mild conditions. This is the first esample of the transformation of coordinated dinitrogen into ammonia by using dihydrogen gas. Activation of dihydrogen gas on the sulfurbridged dimolybdenum complexes [(CpMo)_2S(SR)(S_2CH_2)]^+ and subsequent reactions with the tungsten dinitrogen complex also led to the formation of ammonia.In connection with the structure of the active site of nitrogenase, general synthetic methods for homo-and heterometallic sulfur clusters ranging from trinuclear to pentanuclear clusters was established. A variety of homo-, heterobi-, and heterotrimetallic sulfido clusters containing group 4 -11 metals were systematically synthesized by these rational approaches. Furthermore, these polynuclear complexes were demonstrated to provide multimetallic centers effective for novel activation and transformation of reactivities of small molecules such as alkynes.alkenes. and isocyanides.

研究表明，在温和条件下，由配位不饱和钌配合物和二氢衍生出的阳离子钌二氢配合物trans-[RuCl（H_2）（diphosphine）_2]^+与钨二氮配合物cis-[W（N_2）_2（PMe_2Ph）_4]反应生成氨。这是第一个用氢气将配位二氮转化为氨的例子。氢气对硫桥二钼配合物[（CpMo）_2S（SR）（S_2CH_2）]^+的活化以及随后与钨二氮配合物的反应也导致了氨的生成。结合固氮酶活性中心的结构，建立了从三核到五核的同、异金属硫簇合物的一般合成方法。通过这些合理的合成方法，我们系统地合成了一系列含4 - 11族金属的同、异双和异三金属硫醚簇合物。此外，这些多核配合物被证明提供多金属中心有效的新的活化和转化的小分子，如炔。烯的反应性。和异氰化物。

项目成果

Y.Harada: "Syntheses and Structures of Tungsten Ferrocenyldiazoalkane Complexes Derived from a Dinitrogen Complex" Inorg.Chim.Acta. (in press). (1999)

Y.Harada：“源自二氮络合物的钨二茂铁基重氮烷络合物的合成和结构”Inorg.Chim.Acta。

S.Kuwata: "Structural Diversity of Tetranuclear Tungsten Sulfide Clusters : Syntheses and Crystal Structures of Cluster Containing Raft-Type W_4(μ_3-S)_2(μ-S)_4 and Tetrahedral W_4(μ-S)_6 Cores" J.Chem.Soc.,Dalton Trans.1753-1758 (1997)

S.Kuwata：“四核硫化钨团簇的结构多样性：包含筏型 W_4(μ_3-S)_2(μ-S)_4 和四面体 W_4(μ-S)_6 核的团簇的合成和晶体结构” J.Chem .Soc.，Dalton Trans.1753-1758 (1997)

Y.Ishii: "Selective Hydroforylation of Internal Acetylenes by PdCl_2(PCy_3)_2 : Remarkable Synergistic Effect Cobalt" J.Am.Chem.Soc.119. 6448-6449 (1997)

Y.Ishii：“PdCl_2(PCy_3)_2 对内部乙炔的选择性加氢甲酰化：显着的钴协同效应”J.Am.Chem.Soc.119。

S.Kuwata: "Structures and Reactivities of Diruthenium Dithiolene Complexes and Triruthenium Sulfido Clusters Derived from a Hydrosulfido-Bridged Diruthenium Complex"Organometallics. 17. 3429-3436 (1998)

S.Kuwata：“二钌二硫烯配合物和源自氢硫桥二钌配合物的三钌簇簇的结构和反应性”有机金属化合物。

M.Retbφll: "Dinuclear Pyridine- 1 -Imine-Bridged Rhodium (III) Complexes. Intramolecular Carbon-Hydrogen Bond Activation"Chem.Lett.. 1217-1218 (1998)

M.Retbφll：“双核吡啶-1-亚胺桥铑 (III) 配合物。分子内碳氢键活化”Chem.Lett.. 1217-1218 (1998)