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Construction of Novel Silicon-Transition Metal Multiple Bonds, Elucidation of the Mechanisms for Their Reactions, and Their Expansion to Catalytic Reactions

新型硅过渡金属多重键的构建、反应机理的阐明以及催化反应的扩展

基本信息

批准号：
18350027
负责人：
TOBITA Hiromi
金额：
$ 10.49万
依托单位：
Tohoku University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2006
资助国家：
日本
起止时间：
2006 至 2007
项目状态：
已结题

项目摘要

By a newly developed method, we succeeded in synthesizing the first hydrido (hydrosilylene) ruthenium complex. This complex reacted readily with aldehydes, nitriles, and alkyne to give agostic complexes selectively as primary products. These products are presumed to form through [2+2] cycloaddition between the Ru=Si bond and unsaturated bonds of the substrates followed by partial reductive elimination of the Si-H bond. The complex also reacted smoothly with enones, isocyanates, isothiocyanates, etc. to afford complexes with intriguing structures through [4+2] cycloaddition, hydride migration, C=S bond cleavage, etc.We also succeeded in the synthesis of base-free silyl (silylene) ruthenium complex, and revealed its structure and dynamic behavior. This complex is more reactive than the iron analogue, and addition of a strong Lewis base DMAP resulted in formation of a base-stabilized silyl (silylene) complex was converted to an unprecedented η^<4->sila-o-quinodimethane complex. Moreover, … More the reaction of the silyl (silylene) complex with alcohol surprisingly induced the substitution of all methyl groups on the silyl ligand with alkoxy groups to produce a trialkoxysilyl complex.We demonstrated that the tungsten complexes with an aryl ligand and a silylene ligand underwent 1, 2-aryl migration from the tungsten center to the silylene ligand through formation of η^<3->-silabenzyl complexes as intermediates. The coordinatively unsaturated silyl complexes generated by this migration reacted with nitriles to yield K^<2-> iminoacyl complexes through insertion of a nitrile molecule into the tungsten-silicon bond. The K^<2-> iminoacyl complexes further reacted with another molecule of nitrile to give five-membered metallacycles through ring expansion.By the reaction of a bis (phosphine) platinum complex with sterically congested tribromosilane in the presence of a reducing agent, we succeeded in synthesizing the first (bromosilylene) platinum complex. X-ray crystal structure analysis revealed that this complex has a very short platinum-silicon bond and a completely planar tricoordinate silicon. These facts clearly demonstrate the double bond character of the platinum-silicon boon. We also succeeded in derivation of this complex to a base-stabilized cationic silylyne complex. Less

采用一种新的合成方法，成功地合成了第一个双（硅氢化）钌配合物。该配合物与醛、腈、炔反应，选择性地生成Agostic配合物。推测这些产物是通过Ru=Si键和底物的不饱和键之间的[2+2]环加成，然后部分还原消除Si-H键而形成的。该配合物还与烯酮、异氰酸酯、异硫氰酸酯等通过[4+2]环加成、氢化物迁移、C=S键断裂等反应，得到了结构新颖的配合物，并成功地合成了无碱硅基钌配合物，揭示了其结构和动力学行为。该络合物比铁类似物更具反应性，并且加入强刘易斯碱DMAP导致形成碱稳定的甲硅烷基（亚甲硅烷基）络合物，该络合物被转化为前所未有的η^<4->硅杂-邻-醌二甲烷络合物。此外，委员会认为， ...更多信息令人惊讶的是，甲硅烷基（亚甲硅烷基）配合物与醇的反应导致甲硅烷基配体上的所有甲基被烷氧基取代，产生三烷氧基甲硅烷基配合物。我们证明，具有芳基配体和亚甲硅烷基配体的钨配合物经历了1，2-芳基迁移。通过形成作为中间体的η^ -硅苯基配合物，从钨中心迁移到亚甲硅烷基配体<3->。通过这种迁移产生的配位不饱和甲硅烷基络合物与腈反应，<2->通过将腈分子插入钨-硅键中而产生K2亚氨基酰基络合物。在<2->还原剂存在下，双膦铂配合物与空间拥挤的三溴硅烷反应，成功地合成了第一个（溴硅烯）铂配合物。X射线晶体结构分析表明，该配合物具有很短的铂硅键和完全平面的三配位硅。这些事实清楚地证明了铂-硅布恩的双键特征。我们还成功地将该配合物衍生为碱稳定的阳离子硅炔配合物。少