高等学校化学学报

高等学校化学学报 ›› 2001, Vol. 22 ›› Issue (3): 455.

• 研究论文 • 上一篇    下一篇

改性羰基钴催化氢甲酰化反应系列基元反应的理论研究

雷鸣1, 冯文林2, 徐振锋1, 徐恒连3   

  1. 1. 北京化工大学应用化学系, 北京 100029;
    2. 北京师范大学化学系, 北京 100875;
    3. 中国科学院长春应用化学研究所, 长春 130022
  • 收稿日期:1999-11-30 出版日期:2001-03-24 发布日期:2001-03-24
  • 通讯作者: 冯文林(1940年出生),男,教授,博士生导师,从事量子化学研究.
  • 基金资助:

    国家自然科学基金资助

Theoretical Study on the Mechanisms of Some Elementary Reactions Catalyzed by Modified Carbonyl Cobalt

LEI Ming1, FENG Wen-Lin2, XU Zhen-Feng1, XU Heng-Lian3   

  1. 1. Department of Applied Chemistry, Beijing University of Chemical Technology, Beijing 100029, China;
    2. Department of Chemistry, Beijing Normal University, Beijing 100875, China;
    3. Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
  • Received:1999-11-30 Online:2001-03-24 Published:2001-03-24

PDF (PC)

被引次数

39

摘要： 在HF/LANL2DZ水平下,采用有效核势能近似(ECP)从头算方法,研究了有机膦配体改性羰基钴催化的氢甲酰化反应循环中部分基元反应步骤的微观反应机理.优化了基态势能面上诸反应中间体、过渡态和产物的几何构型.计算了反应活化位垒.结果表明,羰基插入、加氢氧化和脱氢还原的基元反应步骤的活化位垒分别为54.02,134.02和43.44kJ/mol.

关键词: 改性羰基钴, 有机膦配体, 氢甲酰化反应, 从头算, 赝势法

Abstract: All structural geometries of intermediates, transition states and product are optimized at HF/LANL2DZlevel under the effective core potential approximation. The potential energy profile for some elementary reactions of hydroformylation catalyzed by Co 2(CO)6(PH3)2, consisting of carbonyl insertion, H2 oxidative addition and aldehyde reductive elimination, are calculated. The transition states are further confirmed by having one and only one imaginary vibrational frequency. The activation energies of carbonyl insertion, H2 oxidative addition and aldehyde reductive elimination are 54.02, 134.02 and 43.44 kJ/mol, respectively.

Key words: Modified carbonyl cobalt, Organic phosphorus ligand, Hydroformylation, Ab initio method, Effective core potential

中图分类号: 

TrendMD: