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化学学报
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化学学报 ›› 2007, Vol. 65 ›› Issue (8): 715-721. 上一篇    下一篇

研究论文

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

厉嘉云, 彭家建, 邱化玉, 蒋剑雄, 邬继荣, 倪勇, 来国桥   

  1. (杭州师范学院有机硅化学及材料技术教育部重点实验室 杭州 310012)
  • 投稿日期:2006-10-09 修回日期:2006-12-29 发布日期:2007-04-28
  • 通讯作者: 厉嘉云

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

LI Jia-Yun; PENG Jia-Jian; QIU Hua-Yu; JIANG Jian-Xiong; WU Ji-Rong; NI Yong; LAI Guo-Qiao*   

  1. (Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Teachers College, Hangzhou 310012)
  • Received:2006-10-09 Revised:2006-12-29 Published:2007-04-28
  • Contact: LAI Guo-Qiao

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1019

被引次数

12 | 1

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.

关键词: 硅氢化反应, 钌配合物, 铑配合物, 离子液体

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.

Key words: hydrosilylation, rhodium complex, ruthenium complex, ionic liquid