Sigmatropic Rearrangement on M-E Single and Double Bond System (M = Transition Metal, E = Main Group Element

M-E 单键和双键系统上的 Sigmatropic 重排（M = 过渡金属，E = 主族元素

基本信息

批准号：
13440193
负责人：
OGINO Hiroshi
金额：
$ 5.7万
依托单位：
The University of the Air
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2003
项目状态：
已结题

项目摘要

In this research project, we have investigated (1) synthesis of transition-metal complexes with unsaturated bonding between metal and main group elements such as silylene and germylene complexes and (2) reactivities of the unsaturated bonding, especially sigmatropic rearrangement between the M-E and M=E bonds (M = transition metal, E = main group element).Silyl(silylene) complexes have been proposed as key intermediates in many transformations of organosilicon compounds mediated by transition metal compounds. However, such complexes are too unstable to isolate due to the electron-deficient nature of the silylene ligand. We have succeeded to stabilize the silyl(silylene) complexes kinetically using bulky Mes substituents (Mes = 2,4,6-C_6H_2Me_3) and isolated the first silyl(silylene)tungsten, molybdenum, and iron complexes. Reaction of the isolated silyl(silylene)iron complex with 'BuNC afforded a disilanyliron complex produced by 1,3-substituent migration from silyl to silylene ligand followed by 1,2-silyl migration from iron to silylene ligand.Photo-irradiation of Cp^*W(CO)_3Me (Cp^* = η-C_5Me_5) in the presence of (2-N,N-dimethylaminophenyl)dimethylsilane gave a silyl complex in which the amino group was coordinated to the tungsten atom. Further irradiation of the silyl complex caused 1,2-aryl migration from silyl to tungsten to form abase-stabilized silylene complex.Irradiation of phosphinosilyliron complex CpFe(CO)_2SiMe_2PPh_2 afforded a novel metallacycle complex with Fe-Si-P three-membered ring. The Fe-Si bond bears unsaturated character due to the contribution of a resonance form with a phosphino-coordinated silylene ligand. Thus reaction of the complex with acetone proceeded via coordination of acetone oxygen to the silylene ligand followed by insertion into the Si-P bond to form a Fe-Si-O-C-P five-membered ring.

在这个研究项目中，我们研究了（1）金属与主族元素之间具有不饱和键的过渡金属配合物的合成，例如亚甲硅基和甲亚甲基配合物，以及（2）不饱和键的反应性，特别是M-E和M之间的σ重排=E 键（M = 过渡金属，E = 主族元素）。甲硅烷基（亚硅基）配合物已被提议作为有机硅化合物介导的许多转化中的关键中间体然而，由于亚硅基配体的缺电子性质，这种配合物太不稳定而无法分离，我们已经成功地使用大的 Mes 取代基（Mes = 2,4,6）在动力学上稳定了硅基（亚硅基）配合物。 -C_6H_2Me_3) 并分离出第一个硅基(亚硅基)钨、钼和铁络合物。甲硅烷基(亚硅基)铁与'BuNC的配合物通过1,3-取代基从甲硅烷基迁移到亚硅基配体然后1,2-甲硅烷基从铁迁移到亚硅基配体产生二硅烷基铁配合物。Cp^*W(CO的光照射)_3Me (Cp^* = η-C_5Me_5) 在存在的情况下(2-N,N-二甲基氨基苯基)二甲基硅烷得到甲硅烷基络合物，其中氨基与钨原子配位，进一步照射甲硅烷基络合物引起1,2-芳基从甲硅烷基迁移到钨，形成碱稳定的亚甲硅基络合物。 .膦甲硅烷基铁配合物CpFe(CO)_2SiMe_2PPh_2的辐照提供了具有Fe-Si-P三元环的新型金属环络合物由于与膦配位的亚硅基配体的共振形式的贡献而具有不饱和特性，因此络合物与丙酮的反应通过丙酮的配位进行。将氧连接到亚硅基配体上，然后插入Si-P键中，形成Fe-Si-O-C-P五元环。