高等学校化学学报

高等学校化学学报 ›› 1991, Vol. 12 ›› Issue (5): 689.

• 论文 • 上一篇    下一篇

(CH3)3NO存在下M(CO)5(M=Fe,Ru,Os)的CO取代反应动力学研究

申建坤1, 高忆慈1, 史启祯1, Fred Basolo2   

  1. 1. 兰州大学化学系, 730000;
    2. 美国西北大学化学系
  • 收稿日期:1989-09-27 出版日期:1991-05-24 发布日期:1991-05-24
  • 通讯作者: 高忆慈
  • 基金资助:

    国家自然科学基金;国家教委基金;美国国家科学基金

Studies on Kinetics of CO Substitution of M(CO)5(M=Fe,Ru,Os) in the Presence of (CH3)3NO

Shen Jian-kun1, Gao Yi-ci1, Shi Qi-zhen1, Fred Basolo2   

  1. 1. Department of Chemistry, Lanzhou University, Lanzhou, 730000;
    2. Department of Chemistry, Northwestern University, U. S. A.
  • Received:1989-09-27 Online:1991-05-24 Published:1991-05-24

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摘要： 在(CH3)3NO存在下,PPh3取代M(CO)5(M=Fe,Ru,Os)中CO的反应速度遵循二级速度定律,分别与[M(CO)5]和[(CH3)3NO]的一次方成正比,与[PPh3]无关。反应速度按Fe<Ru<Os增大(约增4倍)。

关键词: 羰基取代反应, 动力学, 机理

Abstract: In this paper the kinetics for COsubstitution by PPh3of M(CO)5(M=Fe,Ru,Os) in the presence of catalytic promoter, (CH3)3NO is reported. The rates of reaction are first-order in concentrations of M(CO)Sand of (CH3)3NO but zero-order in PPh3concentration. The reaction rates show an approximate overall four-fold increase in the order Fe < Ru < Os. This is a contrast to the roughly fourty-fold decrease in rate in the order Fe > Ru > Os for the corresponding metal carbonyl cluster, M3(CO)12.

Key words: Reaction of carbonyl substitution, Kinetics, Mechanism

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