Phosphine-stabilized, oxide-supported rhodium catalysts for highly efficient silylative coupling reactions
作者:Shinji Tsukada、Kenji Wada、Hiroki Miura、Saburo Hosokawa、Ryu Abe、Masashi Inoue
DOI:10.1007/s11164-015-1983-8
日期:2015.12
Oxide-supported rhodium catalysts with excellent activity in silylative coupling reactions have been developed. Reductive pretreatment of the catalysts in the presence of 0.5 equiv triphenylphosphine under a hydrogen atmosphere enhanced and stabilized the catalytic activity. Of the catalysts examined, ceria-supported rhodium had the highest activity in the homo-coupling of vinylsilanes to bis(silyl)ethenes
已经开发了在甲硅烷基化偶联反应中具有优异活性的氧化物负载的铑催化剂。在氢气气氛下在0.5当量三苯基膦存在下对催化剂进行还原性预处理可增强并稳定催化活性。在所研究的催化剂中,二氧化铈负载的铑在170℃下乙烯基硅烷与双(甲硅烷基)乙烯的均相偶联中具有最高的活性。氧化锆负载的催化剂通过乙烯基硅烷与苯乙烯在130°C交叉偶联和高周转频率> 8200 h -1选择性地产生 E -1-芳基-2-甲硅烷基在170℃下达到。光谱研究表明,主要在二氧化铈或氧化锆上形成的分散良好的表面铑(I)物种被转化为氢化铑物种,据认为这是高活性的原因。这些催化剂是可循环使用的,而没有损失活性,并且未观察到铑从催化剂中浸出。