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Synthesis and Reactions of Silicon Unsaturated Compounds

硅不饱和化合物的合成与反应

基本信息

批准号：
62470087
负责人：
MITSUO Ishikawa
金额：
$ 3.84万
依托单位：
HIROSHIMA UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1987
资助国家：
日本
起止时间：
1987 至 1988
项目状态：
已结题

项目摘要

We have demonstrated that the reaction of l-mesityl-3-phenyl-1,2-bis(tri-methylsilyl)-1-silacyclopropene with 1 equiv of tetrakis(triethylphosphine)-nickel(0) affords nickelasilacyclobutene (1) in almost quantitative yield. Compound 1 involves a nickel atom and a silicon atom in the four-membered cyclic system and seems to be useful for synthetic chemistry, as well as structural chemistry.Thermolysis of 1 led to the formation of a silapropadiene-nickel complex which underwent further isomerization to give two isomers of a benzodisilacyclo-hexene, 3 and 4, via intramolecular C-H bond activation of a mesityl group. The photolysis of 1 also gave 3 and 4.We have investigated the reaction of 2-phenylethynyl-2-(o-tolyl)hexamethyl-trisilane (2) with a nickel catalyst. Heating 2 with a catalytic amount of tetrakis(triethylphosphine)nickel(0) at 220゜C gave benzodisilacyclohexenes analogous to 3 and 4. Whereas at 260゜C, 2 produced a silylene-nickel complex which could be trapped by methyldiphenylsilane. Similar treatment of 2 with a catalytic amount of an iron-complex in the presence of methyldiphenylsilane as a trapping agent afforded a product arising from insertion of the silylene-iron complex into an Si-H bond of the hydrosilane.

我们已经证明，1-均三甲苯基-3-苯基-1，2-双（三甲基硅烷基）-1-硅环丙烯与1当量的四（三乙基膦）-镍（0）的反应几乎以定量产率得到镍硅环丁烯（1）。化合物1在四元环体系中含有一个镍原子和一个硅原子，似乎对合成化学和结构化学都很有用，1的热分解导致形成硅丙二烯-镍络合物，该络合物通过分子内C-H键活化的均三甲苯基进一步异构化，得到苯并二硅杂环己烯的两种异构体3和4。本文研究了2-苯乙炔基-2-（邻甲苯基）六甲基三硅烷（2）在镍催化剂作用下的反应。将2与催化量的四（三乙基膦）镍（0）在220 ℃下加热，得到类似于3和4的苯并二硅杂环己烯。而在260 ℃时，2生成甲硅烯-镍络合物，该络合物可被甲基二苯基硅烷捕获。在甲基二苯基硅烷作为捕集剂的存在下，用催化量的铁络合物对2进行类似的处理，得到由亚甲硅烷基-铁络合物插入到氢硅烷的Si-H键中而产生的产物。