Synthesis of Polysilanes by Electrochemical Reactions.

对电化学法合成聚硅烷进行了研究。氯硅烷在二甲氧基乙烷中的铜电极体系在一个完整的槽中进行阴极还原，选择性地高产率地得到一些较低的聚硅烷同系物，如二硅烷、三硅烷、四硅烷和五硅烷。1，2-二(氯甲基苯基硅基)乙烷和1，2-二[氯甲基(若甲苯基)硅基]乙烷的类似电解液可得到高相对分子质量的聚二硅烯，其中聚合物主链上不含硅氧键。此外，1，2-二(氯甲基苯基硅基)苯的还原生成了聚(二硅)苯。此外，还研究了氢硅烷高选择性合成氯硅烷。二甲基苯基硅烷、甲基二苯基硅烷和二(正丁基)甲基硅烷分别与2当量的氯化铜和催化量的碘化铜反应，得到相应的三有机氯硅烷。聚氢硅烷如二乙基硅烷、甲基苯基硅烷、苯基硅烷、1，1，2，2-四乙基二硅烷和1，2-二甲基-1，2-二苯基二硅烷与2当量的CuCl2(CuI)试剂反应，选择性地得到相应的一氯氢硅烷，而用4当量的试剂处理则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.