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

甲硅烷基过渡金属配合物：合成、结构、反应性及其催化应用

基本信息

批准号：
15350037
负责人：
SHIMADA Shigeru
金额：
$ 9.47万
依托单位：
National Institute of Advanced Industrial Science and Technology (AIST)
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2003
资助国家：
日本
起止时间：
2003 至 2005
项目状态：
已结题

项目摘要

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.

研究了二齿和三齿硅基配体前体氢硅烷与第10族过渡金属配合物的反应，以推进硅-过渡金属配合物的基础化学，并为Si-Si键形成反应开发有效的催化剂。结果表明，硅-第10族过渡金属配合物的化学性质具有超出预期的多样性。我们还为硅-硅键形成反应催化剂的开发获得了重要信息。本研究的主要结果如下：（2-SiH_3C_6H_4）_2SiH_2与第10族过渡金属配合物的反应，根据金属的种类和配体的空间位阻，得到了不同的产物。本文首次成功地分离和测定了一种硅基镍配合物的结构，该配合物在固态下具有Ni^<IV>（H）（Si）_3结构，而在溶液中具有η^2-（Si-H）Ni结构。我们成功地分离和结构测定的三核和四核钯配合物的钯中心的五个硅原子连接。这是Pd络合物的第一个例子，其中Pd中心被五个形式上的阴离子配体连接。·具有环二硅氧烷部分的Pt络合物的第一个实例通过双齿氢硅烷与Pt（0）膦络合物的反应获得。已阐明，二齿和三齿氢硅烷与第10族过渡金属膦络合物的反应受到膦配体和氢硅烷的空间位阻的高度影响。如果空间位阻小，则容易形成多核络合物和高形式氧化态络合物。另一方面，如果空间位阻严重，则经常发生Si-Si键形成反应。这一发现提供了重要的信息，有效的催化剂的Si-Si键形成反应的发展。