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

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(PPh₃)₃Cl, Ru(PPh₃)₃Cl₂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(BMImBF₆) (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(PPh₃)₃Cl作为反应的催化剂, 在纯离子液体BMImPF₆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(PPh₃)₃Cl, Ru(PPh₃)₃Cl₂催化剂/离子液体BMImPF₆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BMImPF₆的存在提高了过渡金属Rh(PPh₃)₃Cl, Ru(PPh₃)₃Cl₂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.

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

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%, re-spectively. 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.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%, re-spectively. 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.