Silyl-transition-metal complexes : Synthesis, Structure, Reactivity, and Application to Catalysis

具有第10组过渡金属复合体的基本化学进展和硅-过渡金属复合体的原位和三叉戟硅-过渡金属复合体的作用已被研究用于硅-过渡金属复合体的基本化学进展和硅-硅键形成反应的有效催化剂的开发。结果显示，硅-10组过渡金属复合体的化学成分具有超出我们期望的多样性。此外，我们还为硅-硅键形成反应的催化剂的发展提供了重要的信息。本研究的主要结果列出在以下。它澄清了三聚氰胺（2-SiH_3C_6H_4）_2SiH_2的反应，与第10组过渡金属复合体提供了依赖于金属和分子的静态导数的产品的多样性范围。我们第一次在硅镍复合体的隔离和结构确定中获得了解决方案中的Ni^<IV>（H）（Si）_3结构的固态状态下的β ^2-（Si-H）Ni结构。我们成功地利用了三核和四核Pd复合体的隔离和结构确定了五个硅原子的Pd中心。这是由五种正式的非离子配体组成的Pd中心配体的第一个例子。第一个例子是Pt复合物与环氮素动力学是通过与Pt（0）磷酸复合物发生的生物氢化物的反应而产生的。它被澄清，因为具有第10组过渡金属磷酸盐复合体和磷酸盐的静态Hindrance和磷酸盐的三叉戟的反应受到高度影响。“如果静态Hindrance是小的、多核复合体和高正式氧化状态复合体是容易形成的。在另一只手上，如果静态的Hindrance是严重的， Si-Si键形成反应往往需要就位。这为硅-硅键形成反应的有效催化剂的发展提供了重要的信息。

The reaction of bidentate and tridentate silyl ligand precursor hydrosilanes with group 10 transition-metal complexes was studied for the advancement of basic chemistry of silicon-transition-metal complexes and for the development of efficient catalysts for Si-Si bond forming reactions. The results showed that the chemistry of silicon-group 10 transition-metal complexes has a diversity beyond our expectation. Also we obtained important information for the development of catalysts for Si-Si bond forming reaction. The major results of this research are listed below.It was clarified that the reaction of the tridentate hydrosilane, (2-SiH_3C_6H_4)_2SiH_2,with group 10 transition-metal complexes provided diverse range of products depended on the metals and the steric hindrance of the ligands. We for the first time succeeded in the isolation and structure determination of a silylnickel complex that has a Ni^<IV>(H)(Si)_3 structure in the solid state while η^2-(Si-H)Ni structure in solution.・We succeeded in the isolation and structure determination of trinuclear and tetranuclear Pd complexes having Pd centers ligated by five Si atoms. This is the first example of Pd complex with a Pd center ligated by five formally anionic ligands.・The first example of Pt complex with cyclodisiloxane moiety was obtained by the reaction of the bidentate hydrosilane with a Pt(0) phosphine complex.・It was clarified that the reaction of the bidentate and the tridentate hydrosilanes with group 10 transition metal phosphine complexes was highly affected by the steric hindrance of phosphine ligands and of the hydrosilanes. If the steric hindrance is small, multinuclear complexes and high formal oxidation state complexes are easily formed. On the other hand, if the steric hindrance is severe, Si-Si bond forming reaction often takes place. This finding provides important information for the development of efficient catalysts for a Si-Si bond forming reaction.