Synthesis of Polysilanes by Electrochemical Reactions.

研究了电化学合成聚硅烷的方法。在未分裂的二甲氧基乙烷中使用铜电极体系阴极还原氯硅烷，可选择性地获得一些低聚硅烷同系物，如二硅烷、三硅烷、四硅烷和五硅烷，收率高。1,2-二（氯甲基苯基硅基）乙烷和1,2-二（氯甲基苯基硅基）乙烷的类似电解反应可以得到具有高分子量的聚（二苯基）乙烷，其中聚合物主链中不包括硅氧键。此外，1,2-二-（氯甲基苯基硅基）苯的还原得到聚（二硅基）苯。研究了由氢硅烷合成高选择性氯硅烷的方法。二甲基苯基硅烷、甲基二苯基硅烷和二（正丁基）-甲基硅烷与2等量的氯化铜和催化量的碘化铜反应得到三有机氯硅烷。二乙基硅烷、甲基苯基硅烷、苯基硅烷、1,1,2,2-四乙基二硅烷、1,2-二甲基-1,2-二苯基二硅烷等聚氢硅烷与2个等量CuCl_2（CuI）试剂反应可选择性地得到相应的单氯氢硅烷，而与4个等量CuCl_2（CuI）试剂反应可得到唯一的二氯硅烷。

Synthesis of polysilanes by electrochemical method has been investigated. Cathodic reduction of chlorosilanes with the use of copper electrode system in dimethoxyethane in an undivided cell afforded some lower homologues of polysilanes such as disilanes, trisilanes, tetrasilanes, and pentasilanes selectively in high yields. Similar electrolyses of 1,2-bis(chloromethylphenylsilyl)ethane and 1,2-bis[chloromethyl(rho-tolyl)silyl]ethane afforded poly(disilanylene)ethylenes with high molecular weights, in which no siliconoxygen bonds in the polymer backbone are included. Moreover, reduction of 1,2-bis- (chloromethylphenylsilyl)benzene afforded poly(disilanylene)phenylene.A highly selective synthesis of chlorosilanes from hydrosilanes has also been investigated. The reaction of dimethylphenylsilane, methyldiphenylsilane, and di(n-butyl)- methylsilane with 2 equiv of copper(II) chloride and a catalytic amount of copper(I) iodide afforded the respective triorganochlorosilanes. Similar reactions of polyhydrosilanes such as diethylsilane, methylphenylsilane, phenylsilane, 1,1,2,2-tetraethyldisilane, and 1,2- dimethyl-1,2-diphenyldisilane with 2 equiv of the CuCl_2(CuI) reagent gave the corresponding monochlorinated hydrosilanes selectively, while treatment with 4 equiv of the reagent afforded dichlorosilanes as the sole product.