Abstract：
The preparation of cationic bis(hydrosilane)-coinage-metal complexes by chloride abstraction from the neutral metal chloride precursors with Na[BArF4] is described. Unlike previously reported hydrosilane-stabilized copper and silver complexes, the presented complexes are cationic and feature two bidentate ortho-(silylphenyl)phosphine ligands. These complexes were fully characterized by NMR spectroscopy and X-ray diffraction analysis, revealing that both Si-H bonds are activated by the Lewis acidic cationic metal center. The new complexes were found to be effective in catalytic carbonyl hydrosilylation, leading to the corresponding silyl ethers under mild conditions without the addition of an external base. Combined mechanistic control experiments and quantum chemical calculations support an ionic outer-sphere mechanism, in which a neutral metal alkoxide species instead of a metal hydride is the key intermediate that interacts with the silylcarboxonium ion to generate the silyl ether.
摘要：
描述了通过用Na[BArF4]从中性金属氯化物前体中提取氯化物来制备阳离子双（氢硅烷）-硬币-金属配合物的方法。与先前报道的氢硅烷稳定的铜和银络合物不同，所提出的配合物是阳离子的，并具有两个二齿邻-（甲硅烷基苯基）膦配体。这些配合物通过NMR光谱和X射线衍射分析进行了充分表征，揭示了两个Si-H键都被路易斯酸性阳离子金属中心激活。新的配合物被发现是有效的催化羰基氢化硅烷化，在不添加外部碱的温和条件下得到相应的甲硅烷基醚。机械控制实验和量子化学计算相结合，支持离子外球机制，其中中性金属醇盐物质而不是金属氢化物是与甲硅烷基羧基离子相互作用产生甲硅烷基醚的关键中间体。
