催化学报

催化学报 ›› 2010, Vol. 31 ›› Issue (6): 656-660.

• 研究论文 • 上一篇    下一篇

含膦和含氮配体功能化离子液体中 RuCl3•3H2O 催化分子氧氧化醇

周成亮, 刘晔   

  1. 华东师范大学化学系上海市绿色化学与化工过程绿色化重点实验室, 上海 200062
  • 收稿日期:2010-06-25 出版日期:2010-06-25 发布日期:2013-12-05

Selective Oxidation of Alcohols with Molecular Oxygen Catalyzed by RuCl3•3H2O in P- and N-Containing Ligand Functionalized Ionic Liquids

ZHOU Chengliang, LIU Ye*   

  1. Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of Chemistry, East China Normal University, Shanghai 200062, China
  • Received:2010-06-25 Online:2010-06-25 Published:2013-12-05

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摘要： 无共氧化剂参与条件下, 以氧气为氧化剂, 在含膦或含氮配体功能化离子液体和普通离子液体 (溶剂) 组成的混合体系中, RuCl3•3H2O 能有效催化多种醇的选择氧化, 高选择性地生成相应的醛或酮. 其中, 配位能力较弱的含氮配体功能化离子液体更有利于提高钌催化剂的活性和选择性, 但体系无法有效实现钌催化剂的循环使用. 配体功能化离子液体本身的氧化降解是导致钌催化剂失活的根本原因.

关键词: 功能化离子液体, 钌催化剂, 配体, 醇氧化, 分子氧

Abstract: The application of functionalized ionic liquids (ILs) in homogeneous catalysis facilitates the reaction efficiency in homogeneous phase, liquid-liquid separation, and IL solvent-catalyst recycling. In this work, a series of P- or N-containing ligand functionalized imida-zolium-based ILs were synthesized and used in conjunction with common ambient imidazolium-based ILs to afford the IL solution, which acted as both the ligand and the solvent. In such functionalized IL compositions, RuCl3•3H2O catalyzed oxidation of various alcohols using O2 to aldehydes and ketones was achieved with high selectivity (most above 95%) in the absence of co-oxidants. The catalytic performance of the RuCl3•3H2O catalyst was greatly influenced by the solvents and ligands. The N-containing ligand functionalized IL with weaker liga-tion to Ru center exhibited better activity and much higher selectivity. Whereas, the N,P-hybrid ligand functionalized IL with bidentate che-lating ability to Ru center showed relatively low activity. However, the recyclability of RuCl3•3H2O in such functionalized IL compositions was unavailable. The in situ 31P NMR spectroscopy study indicated that the oxidative degradation of the ligand itself was responsible for the deactivation of the Ru catalyst.

Key words: functionalized ionic liquid, ruthenium catalyst, ligand, alcohol oxidation, molecular oxygen