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化学学报
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化学学报 ›› 2010, Vol. 68 ›› Issue (03): 217-221. 上一篇    下一篇

研究论文

乙基桥联有序介孔有机硅负载Pd(II)有机金属催化剂用于水介质Barbier反应

杨旭石1，黄建林2，朱凤霞2，李和兴*,1,2   

  1. (1华东理工大学化学与分子工程学院 上海 200237)
    (2上海师范大学化学系 上海 200234)
  • 投稿日期:2009-06-04 修回日期:2009-07-26 发布日期:2010-02-20
  • 通讯作者: 李和兴 E-mail:hexing-li@shnu.edu.cn
  • 基金资助:

    国家自然科学基金

Ethyl-bridged Periodic Mesoporous Organosilica Supported Pd(II) Organometallic Catalyst for Water-medium Barbier Reaction

Yang Xushi1 Huang Jianlin2 Zhu Fengxia2 Li Hexing*,1,2   

  1. (1 School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237)
    (2 Department of Chemistry, Shanghai Normal University, Shanghai 200234)
  • Received:2009-06-04 Revised:2009-07-26 Published:2010-02-20
  • Contact: HeXing Li E-mail:hexing-li@shnu.edu.cn

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被引次数

16 | 5

以PPh2C2H4-Si(OEt)3和(EtO)3Si-C2H4-Si(OEt)3为混合硅源, 在表面活性剂作用下共缩聚制备有序介孔有机硅杂化材料, 再络合Pd(II)离子得到固载化Pd(II)非均相催化剂. 在水介质Barbier反应中, 所制备的Pd(II)-PPh2-PMO(Et)具有与均相Pd(PPh3)2Cl2催化剂相当的催化活性, 主要归因于高比表面积、有序介孔结构, 有利于提高Pd(II)活性位分散度, 减少传质阻力, 同时乙基修饰孔壁增强表面疏水性, 有利于有机分子在孔道内的扩散和活性位上的吸附, 导致高催化活性, 而且可重复使用, 显示了良好的工业应用前景.

关键词: 有序介孔有机硅, Pd(PPh3)2Cl2, 非均相催化剂, Barbier反应, 水介质有机合成

Ordered mesoporous organometallic catalyst Pd(II)-PPh2-PMO(Et) was synthesized by coordinating the Pd(II) with PPh2-ligand originally incorporated into the ethyl-bridged periodic mesoporous organosilica via surfactant-directed co-condensation. This catalyst exhibited matchable activity with the corresponding PdCl2(PPh3)2 homogeneous catalyst in water-medium Barbier reaction. On one hand, it could be attributed to the large surface area and ordered mesporous channels of the PMO support, leading to the high dispersion of Pd(II) active sites and the reduced diffusion limit. Meanwhile, the ethyl fragments embedded in the pore walls could enhance surface hydrophobility, which further promoted the diffusion and adsorption of organic molecules, leading to the enhanced activity. Besides, the Pd(II)-PPh2-PMO(Et) could be used repetitively, showing a good potential in industrial applications.

Key words: periodic mesoporous organosilica, Pd(PPh3)2Cl2, immobilized homogeneous catalyst, Barbier reaction, water-medium clean organic reaction