有机硅聚合物负载双齿型硫铂配合物的合成及其催化性能

SYNTHESIS OF POLYSILSESQUIOXANE - SUPPORTED BIDENATE SULFIDE PLATINUM COMPLEX AND ITS CATALYTIC PROPERTY

β-氯乙基烯丙基硫醚与γ-巯丙基三甲氧基硅烷钠盐在甲苯中缩合,得到4,7-二硫杂癸烯-9-基三甲氧基硅烷,后者以气相法二氧化硅水解固载,再与氯亚铂酸钾反应,得到二氧化硅固载聚-4,7-二硫杂癸烯-9-基倍半硅氧烷铂配合物,该配合物能催化多种烯烃与兰乙氧基硅烷的硅氢加成反应,而且用量可低至烯烃摩尔量的十万分之一。

The synthesis, characterization, and catalytic behavior of a new kind of hydrosilylation catalyst, poly-4,7-dithiadecen-9-ylsilsesquioxane platinum complex have been described. By condensation of 3—chloroethylthiopropylene with sodium 3-trimethoxysilylpropyl mercaptide in toluene, 4,7-dithiadecen-9-yltrimethoxysflane was obtained in 43% yield. The later was subjected to hydrolysis and immobilization on fumed silica, followed by reacting with potassium chloroplatinite under Ar atmosphere in acetone to give the title Complex. It was found that it is an effective catalyst for the hydrosilylation of olefins with triethoxysilane. Even if the amount of the complex used was lowered to the molar ratio of 10^(-5) to the olefin, the hydrosilylation reaction took place still smoothly. The turnover number was more than 60,000 in such a case. The structure of the title complex Was discussed. The influences of temperature, the amount of the complex used, and the nature of olefin used on the catalytic activity and selectivity of the complex were investigated also.