机构地区: 杭州师范学院材料与化学化工学院有机硅化学及材料技术教育部重点实验室
出 处: 《化学学报》 2007年第8期715-721,共7页
摘 要: 研究了在室温离子液体以及室温离子液体/有机溶剂复合介质体系中,Rh(PPh_3)_3Cl,Ru(PPh_3)_3Cl_2等催化烯烃与三乙氧基硅烷的硅氢加成反应.实验结果表明,在乙二醇二甲醚/离子液体1-丁基-3-甲基咪唑六氟磷酸盐(BMImBF_6)(V/V =1/4)介质中,于90℃下,己烯与三乙氧基硅烷反应的转化率为100%,β加成物的选择性可达89.0%,而用Rh(PPh_3)_3Cl作为反应的催化剂,在纯离子液体BMImPF_6中,就可以高效催化烯烃与三乙氧基氢硅烷的加成反应,过渡金属Rh(PPh_3)_3Cl,Ru(PPh_3)_3Cl_2催化剂/离子液体BMImPF_6催化体系,不仅解决了产物与催化剂分离困难这一难题,同时,离子液体BMImPF_6的存在提高了过渡金属Rh(PPh_3)_3Cl,Ru(PPh_3)_3Cl_2催化硅氢加成反应的活性,特别是β加成物的选择性。反应结束后,催化剂/离子液体与产物易于分离,并且可以重复使用。 Alkene hydrosilylation catalyzed by Ru(PPh3)3Cl2 in ionic liquids/organic solvents and Rh(PPh3)3Cl in ionic liquids was studied in this paper. Both catalytic activity and selectivity of Ru(PPh3)3Cl2 were improved in ionic liquid BMImPF6/DME medium. The conversion of hexene and selectivity of β-adduct for the hydrosilylation reaction of 1-hexene with triethoxysilane catalyzed by Ru(PPh3)3Cl2 in ionic liquid BMImPF6/DME (V/V= 1/4) medium at 90 ℃ were 100% and 89.0%, respectively. While the conversion of hexene and selectivity to β-adduct catalyzed by Rh(PPh3)3Cl in sole BMImPF6 at 90℃ were 100% and 99.9%, respectively. The Rh(PPh3)3Cl in BMImPF6 catalyst system could be recovered easily and be reused more than three times without noticeable loss of its catalytic activity and selectivity.