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

通过一种新的方法，我们成功地合成了一氢(硅烯)Ru络合物。该络合物很容易与醛、腈和炔反应，选择性地生成络合物作为初级产物。这些产物被认为是通过Ru=Si键和衬底的不饱和键之间的[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，得到了结构有趣的配合物。我们还成功地合成了无碱硅基(硅烯)Ru配合物，揭示了其结构和动力学行为。该络合物比铁类似物具有更强的活性，加入强路易斯碱二甲基亚胺形成了碱稳定的硅基(硅烯)络合物，并转化为前所未有的η^&lt；4-&gt；Sila-o-quinodi甲烷络合物。此外，…此外，硅基(硅烯)配合物与醇的反应意外地诱导硅基上的所有甲基被烷氧基取代生成三烷氧基硅基配合物。我们证明了具有芳基和硅烯配体的钨配合物通过形成η^&lt；3-&gt；-硅苯基配合物作为中间体，从钨中心向硅烯配体迁移。这种迁移生成的配位不饱和硅基配合物通过在钨-硅键上插入一个腈分子而与腈反应生成K^&lt；2-&gt；亚氨基酰基配合物。K^&lt；2-&gt；亚氨基酰基配合物通过扩环进一步与另一种丁腈分子反应生成五元金属环，通过双膦铂配合物与空间拥挤的三溴硅烷在还原剂存在下的反应，我们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，该络合物具有很短的铂-硅键和完全平面的三配位硅。这些事实清楚地证明了铂-硅恩惠的双键特性。我们还成功地将该络合物衍生为碱基稳定的阳离子硅炔络合物。较少

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