高等学校化学学报

高等学校化学学报 ›› 1988, Vol. 9 ›› Issue (10): 1035.

• 论文 • 上一篇    下一篇

Os3(CO)12及其膦取代衍生物氧原子转移反应动力学与机理研究

申建坤1, 高忆慈1, 史启祯1, Fred Basolo2   

  1. 1. 兰州大学化学系;
    2. 美国西北大学化学系
  • 收稿日期:1987-04-28 出版日期:1988-10-24 发布日期:1988-10-24
  • 通讯作者: 史启祯
  • 基金资助:

    中国自然科学基金;美国国家科学基金

Kinetics and Mechanism of Oxygen Atom Transfer Reactions to Os3(CO)12 and Its Phosphine Substituted Derivatives

Shen Jiankun1, Gao Yici1, Shi Qizhen1, Fred Basolo2   

  1. 1. Department of Chemistry, Lanzhou University, Lanzhou;
    2. Department of Chemistry, Northwestern University, Evanston, Hlinois 60201, U.S.A
  • Received:1987-04-28 Online:1988-10-24 Published:1988-10-24

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摘要： 报道了(CH3)3NO存在条件下Os3(CO)12和Os3(CO)11L(L=PPh3,P(n-Bu)3,AsPh3)分别在CH2Cl2-C2H5OH和CH2Cl2溶剂中职代羰基反应的动力学数据。结果表明,反应遵循单项缔合速度定律,与外来配体L的浓度无关。定量地研究了溶剂中乙醇的浓度对反应速度的影响,并讨论了反应机理、过渡态和中间体可能的结构及取代配体的影响。

关键词: 十二羰基合三锇, 三甲基胺氧化物, 氧原子转移, 动力学与机理

Abstract: Detailed kinetic data are reported for the reactions of COsubstitution of Os3(CO)12 and Os3(CO)11L (where L = PPh3, AsPh3, P(n-Bu)3) in CH2Cl2-C2H5OH and CH2Cl2 respectively in the presence of Me3NO. The results indicate that the reactions follow associative rate law, that is, r = k2[complex][Me3NO], and are independent of entering ligand concentration. The effect of C2H5OH as solvent on the reactions has been investigated quantitatively. Reaction mechanism, structures of transition states and intermediates have been proposed. The ligand effects on the reactions have been discussed as well.

Key words: Triosmium dodecacarbonyl, Trimethylamine N-Oxide, Oxygen atom transfer, Kinetics and mechanism

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