过渡金属钌、铑配合物在室温离子液体中催化硅氢加成反应的研究

Study on Hydrosilylation Catalyzed by Transition Metal Rhodium and Ruthenium Complexes in Ionic Liquids

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.