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化学学报
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化学学报 ›› 1992, Vol. 50 ›› Issue (10): 978-982. 上一篇    下一篇

研究论文

茂基钌化合物的合成与结构研究:双核钌氢合物的合成与晶体结构研究

来鲁华;张泽莹;邵美成   

  1. 北京大学化学系
  • 发布日期:1992-10-15

The synthesis and structure studies on cyclopentadienylruthenium derivatives:the crystal structure of [(C~5H~5)Ru(PPh~3)(μ-H)]~2

LAI LUHUA;ZHANG ZEYING;SHAO MEICHENG   

  • Published:1992-10-15

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三氢钌化物[(C~5H~5)Ru(PPh~3)H~3](1)经光解反应生成了一个双核钌氢化合物[(C~5H~5)Ru.(PPh~3)(μ-H)]~2(2).用X射线重原子法及Fourier迭代解出了2的晶体结构,其分子呈二聚形式,Ru-Ru键处在对称中心,两个钌原子间还通过两个桥氢原子相联,该二聚体的单体为16电子物种,与推测的碳氢键活化反应的中间体类似,为金属有机氢化物活化碳氢键的反应历程提供了证据.文中还给出了2的可能形成过程.

关键词: 晶体结构测定, 反应机理, 三苯基膦, 光解反应, 茂基钌氢化合物, 双核钌氢化合物, 三氢钌化物

Title compound (I) was obtained from photolysis of (C5H5)Ru(PPh3)H3. The dimer mol. of I possesses point symmetry with the symmetry center on the middle of Ru-Ru bond. Each Ru atom bonded to one Ru atom, one cyclopentadienyl ring, one PPh3, and two bridged hydride ligands. The monomer form of the dimer is a 16-electron species similar to the proposed intermediate in C-H bond activation reaction, e.g. (C5Me5)Ir?PMe3). Here the 16-electron species were catched in the dimer form, giving an experimental evidence to the proposed mechanism of C-H bond activation reaction by organometallic hydrides. The possible path for the formation of I was also suggested.

Key words: CRYSTAL STRUCTURE DETERMINATION, REACTION MECHANISM, TRIPHENYLPHOSPHINE, PHOTOLYTIC REACTION

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