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化学学报
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化学学报 ›› 2008, Vol. 66 ›› Issue (9): 1009-1014.    下一篇

研究论文

Rh(PPh3)3Cl/有机融盐催化烯烃硅氢加成反应

厉嘉云，彭家建，吴慧，白赢，邱化玉*，蒋剑雄，来国桥*   

  1. (杭州师范大学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:2007-09-27 修回日期:2007-12-05 发布日期:2008-05-14
  • 通讯作者: 来国桥

Hydrosilylation of Alkenes Catalyzed with Rh(PPh3)3Cl/Organic Molten Salt

LI Jia-Yun PENG Jia-Jian WU Hui BAI Ying QIU Hua-Yu* JIANG Jian-Xiong LAI Guo-Qiao*   

  1. Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou 310012)
  • Received:2007-09-27 Revised:2007-12-05 Published:2008-05-14
  • Contact: LAI Guo-Qiao

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研究了Rh(PPh3)3Cl/二烷基咪唑六氟磷酸盐或烷基吡啶六氟磷酸盐催化三乙基氢硅烷与烯烃的硅氢加成反应. 实验结果表明, 二烷基咪唑六氟磷酸盐或烷基吡啶六氟磷酸盐的存在既有利于提高加成反应的转化率和β加成物的选择性, 又有利于反应结束后产物与催化剂的分离. C16PyPF6作为催化剂的载体, Rh(PPh3)3Cl催化苯乙烯与三乙基氢硅烷加成反应的转化率为95.7%, β加成物的选择性为87.8%, α加成物的选择性为0.001%, 脱氢加成产物的选择性为9.2%. 同时, 此催化剂重复使用7次以后仍具有较高的活性.

关键词: Rh(PPh3)3Cl, 二烷基咪唑六氟磷酸盐, 烷基吡啶六氟磷酸盐, 硅氢加成反应, 三乙基硅烷

The activity and selectivity influenced by Rh(PPh3)3Cl/dialkylimidazolium hexafluorophosphate or N-alkylpyridinium hexafluorophosphate have been investigated in the hydrosilylation of olefin with triethylsilane. It was found that both conversion and selectivity to β-product could be improved, but the selectivities to α-product and unsaturated product decreased by using this catalyst. The Rh(PPh3)3Cl/C16PyPF6 exhibited the highest selectivity to β-product in the hydrosilylation of styrene by triethylsilane. The conversion of styrene was 95.7%, the selectivity to β-product was 87.8%, the selectivity to α-product was 0.001%, and the selectivity to unsaturated product was 9.2%. At the same time, this catalyst might be reused more than seven times without noticeable loss of its catalytic activity.

Key words: Rh(PPh3)3Cl, dialkylimidazolium hexafluorophosphate, N-alkylpyridinium hexafluorophosphate, hydrosilylation, triethylsilane