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Synthesis of Stable Silylene and Germylene Complexes and the Mechanistic Studies on Catalytic Reactions Utilizing Them

稳定的亚硅基和亚甲锗烷基配合物的合成及其催化反应机理研究

基本信息

批准号：
09440223
负责人：
OGINO Hiroshi
金额：
$ 8.38万
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：
1997
资助国家：
日本
起止时间：
1997 至 1998
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09440223/
关键词：
SILYLENE COMPLEX SILYL (SILYLENE) COMPLEX BIS (SILYLENE) COMPLEX GERMYLENE COMPLEX 1,3-MIGRATION CATALYTIC REACTION REDISTRIBUTION REACTION METHYLATION シリリン錯体

项目摘要

(1) Using tungsten as a central metal, donor-bridged bis(silylene) complexes, external donor-stabilized silyl(silylene) complexes, dimeric silyl(silylene) complexes in which the oxygen atoms of carbonyl ligands are mutually coordinated to the silylene ligands to form an eight-membered ring, and donor-free germyl(germylene) complexes were synthesized by photolysis of carbonyl complexes. The structures of these complexes have been determined by X-ray crystallography. 1,3-Migration of substituents was demonstrated to occur on isolated silyl(silylene) complexes.(2) Reactivity of bis(silylene)ruthenium complexes was studied, and high electrophilicity of silylene ligands was proved based on their high reactivity toward alcohols and water, and the intramolecular C-H bond activation by the Si-Ru double bond. Dimethylsilylene was found to add to bis(silylene)ruthenium and iron complexes to give disilanyl(silylene) complexes.(3) By means of iridium complexes having a (phosphinoethyl)silyl ligand, we found the following new reactions ; redistribution of substituents on hydrodisilanes, formation of SiR(Me)H2 by transfer of a methyl group from a methyl(hydrido)iridium complex to RSiH3, formation of a hydrido(silylene) complex via 1,2-hydrogen sift from a hydrosilyl ligand to a coordinatively unsaturated metal center, etc.(4) We newly prepared some donor-stabilized cationic germylene complexes and diiron and iron-tungsten complexes bridged by a secondary alkyl-substituted silylene ligand.(5) The first 1 , 2-phenylenedioxysilyl iron complex was synthesized, the structure determined, and the reactivity investigated.(6) As the new reactions of silyl(carbonyl)iron complexes, we found the reaction with LiAlH_4 leading the reduction of a CO ligand and coupling with a silyl group. to give a methylsilane, and the reaction with trialkylphosphites giving acyl complexes.

(1)以钨为中心金属，通过光解反应合成了给电子体桥联的双(硅烯)络合物、外给电子体稳定的硅基(硅烯)络合物、氧原子与硅烯配体相互配位形成八元环的二聚硅基(硅烯)络合物和无给电子体的锗(锗)络合物。用X-射线单晶衍射法测定了它们的结构。(2)研究了双(硅烯)Ru配合物的反应活性，证明了硅烯配体对醇和水的高亲电性，并通过Si-Ru双键激活了分子内的C-H键。二甲基硅烯被发现与双(硅亚甲基)Ru和铁的络合物形成二硅基(硅烯)络合物。(3)通过具有(膦乙基)硅基配体的Ir络合物，我们发现了以下新的反应；氢二硅烷上取代基的重新分配，甲基(氢化)Ir络合物向RSiH3的甲基转移生成SIR(Me)H_2，氢化硅基配体通过1，2-氢筛到配位不饱和金属中心形成氢化(硅烯)络合物等。(4)我们新合成了一些给体稳定的阳离子锗络合物和通过二次烷基取代硅烯配体桥联的二铁和铁-钨络合物。(5)合成了第一个1，2-苯二氧基铁络合物，确定了其结构，并研究了其反应活性。我们发现与LiAlH_4的反应导致了CO配体的还原，并与硅基发生偶联。得到甲基硅烷，与三烷基亚磷酸盐反应得到酰基络合物。