高等学校化学学报

高等学校化学学报 ›› 1989, Vol. 10 ›› Issue (3): 322.

• 研究简报 • 上一篇    下一篇

M3(CO)12(M=Fe,Ru,Os)的氧原子转移反应动力学

申建坤1, 师颜龙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:1987-09-16 出版日期:1989-03-24 发布日期:1989-03-24
  • 通讯作者: 史启祯
  • 基金资助:

    中国科学院科学基金

Kinetics and Mechanism of Oxygen Atom Transfer Reactions to M3(CO)12(M =Fe,Ru,Os)

Shen Jiankun1, Shi Yianlong1, Gao Yici1, Shi Qizhen1, Fred Basolo2   

  1. 1. Department of Chemistry, Lanzhou University, Lanzhou;
    2. Department of Chemistry, Northwest University, Evanston, I11, USA
  • Received:1987-09-16 Online:1989-03-24 Published:1989-03-24

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摘要： 近期研究表明,M(CO)6(M=Cr,Mo,W)与Me3NO作用是缔合反应,Me3NO中氧原子亲核进攻羰基碳,使其以CO2的形式脱离金属原子,由此产生的活性中间体M(CO)5与外来配体快速反应生成M(CO)5L。

关键词: 氧化三甲基胺, 金属羰基化合物, 动力学与机理

Abstract: Quantitative investigations are reported for the reactions of the triangular clusters M3(CO)12(M=Fe, Ru, Os) with trimethyl amine N-oxide in the presence of phosphorous ligand. The rates of the reactions are first orders in concentrations of M3(CO)12and of Me3NO, but zero-order in entering ligand concentration. The rates of the reactions decrease in the order Fe>Ru>Os. Amechanism is proposed which involves attack on carbonyl carbon with the formation of coordinatively unsaturated intermediates of the type M3(CO)11, which then rapidly react with the entering ligand.

Key words: Trimethyl amine N-oxide, Metal carbonyls, Kinetics and mechanism

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