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化学学报
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化学学报 ›› 2007, Vol. 65 ›› Issue (20): 2320-2324. 上一篇    下一篇

研究论文

单氢钌配合物与水和2,2,2-三氟乙醇的作用机理

尹传奇1,2，陈瑶2，冯权武2，柏正武2，王长芳2，李早英*,1   

  1. (1武汉大学化学与分子科学学院 武汉 430072)
    (2武汉工程大学化工与制药学院 武汉 430074)
  • 投稿日期:2007-02-08 修回日期:2007-04-26 发布日期:2007-10-28
  • 通讯作者: 李早英

Interaction Mechanisms of Ruthenium Hydride Complex with Water and 2,2,2-Trifluoroethanol

YIN Chuan-Qi1,2； CHEN Yao2； FENG Quan-Wu2； BAI Zheng-Wu2 ；WANG Chang-Fang2； LI Zao-Ying*,1   

  1. (1 College of Chemistry & Molecular Sciences, Wuhan University, Wuhan 430072)
    (2 College of Chemical Engineering & Pharmacy, Wuhan Institute of Technology, Wuhan 430074)
  • Received:2007-02-08 Revised:2007-04-26 Published:2007-10-28
  • Contact: LI Zao-Ying

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1082

被引次数

10

利用原位1H和31P NMR对单氢钌配合物TpRu(PPh3)(CH3CN)H [Tp＝hydrotris(pyrazolyl)borate]与H2O和酸性HOCH2CF3的反应进行了研究, 结果显示相应的反应产物分别是TpRu(PPh3)(CH3CN)(OH) 和TpRu(PPh3)(CH3CN)(OCH2CF3). 观察到反应过程中Ru—H…HOH和Ru—H…HOCH2CF3分子间的氢键作用. 提出了生成TpRu(PPh3)(CH3CN)(OH)和TpRu(PPh3)(CH3CN)(OCH2CF3)的不同作用机理. 在水存在下, TpRu(PPh3)(CH3CN)H 与H2O反应, 经过中间体TpRu(PPh3)(H2O)H和TpRu(PPh3)(OH)(η2-H2)生成产物TpRu(PPh3)(CH3CN)(OH). 而TpRu(PPh3)(CH3CN)H与酸性HOCH2CF3反应时, 单氢配体被质子化形成中间体[TpRu(PPh3)(CH3CN)- (η2-H2)](OCH2CF3), 进而转变成产物TpRu(PPh3)(CH3CN)(OCH2CF3). TpRu(PPh3)(CH3CN)(OCH2CF3)与H2作用, 经中间体TpRu(PPh3)(HOCH2CF3)H生成TpRu(PPh3)(η2-H2)H.

关键词: 单氢钌配合物, 原位核磁共振, 分子间氢键, 反应中间体, 反应机理

In situ 1H and 31P NMR methods were used to study the reactions of ruthenium hydride complex TpRu(PPh3)(CH3CN)H [Tp＝hydrotris(pyrazolyl)borate] with water and acidic HOCH2CF3. The result shows that the the products were TpRu(PPh3)(CH3CN)(OH) and TpRu(PPh3)(CH3CN)(OCH2CF3), respectively. The presence of Ru—H…HOH and Ru—H…HOCH2CF3 dihydrogen-bonding interactions was observed. The different mechanisms involving the formation of TpRu(PPh3)(CH3CN)(OH) and TpRu(PPh3)(CH3CN)(OCH2CF3) are proposed. In the presence of water, TpRu(PPh3)(CH3CN)H reacts with H2O to produce TpRu(PPh3)(CH3CN)(OH) via the intermediates TpRu(PPh3)(H2O)H and TpRu(PPh3)(OH)(η2-H2). However, in the case of CF3CH2OH, the protonation of the hydride ligand by CF3CH2OH generates a key species [TpRu(PPh3)(CH3CN)(η2-H2)](OCH2CF3), which is then transformed to TpRu(PPh3)(CH3CN)(OCH2CF3). TpRu(PPh3)(CH3CN)(OCH2CF3) reacts with H2 to result in the formation of TpRu(PPh3)(η2-H2)H via the intermediate TpRu(PPh3)(HOCH2CF3)H

Key words: ruthenium hydride complex, in situ NMR, intermolecular hydrogen bond, reaction intermediate, reaction mechanism