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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
【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(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。
【Abstract】 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 ofβ-adduct for the hydrosilylation reaction of 1-hexene with triethoxysilane catalyzed by Ru(PPh3)3Cl2 in ionic liquid BMImPF6DME (V/V=1/4) medium at 90℃were 100% and 89.0%,respectively.While the conver- sion of bexene and selectivity toβ-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 re- used more than three times without noticeable loss of its catalytic activity and selectivity.
【Key words】 hydrosilylation; rhodium complex; ruthenium complex; ionic liquid;
- 【文献出处】 化学学报 ,Acta Chimica Sinica , 编辑部邮箱 ,2007年08期
- 【分类号】O643.32
- 【被引频次】8
- 【下载频次】436