物理化学学报 >> 2000, Vol. 16 >> Issue (06): 522-526.doi: 10.3866/PKU.WHXB20000609

研究论文 上一篇    下一篇

羟基钴催化氢甲酰化反应的理论研究

雷鸣, 冯文林, 徐振峰   

  1. 北京化工大学应用化学系，北京 100029|北京师范大学化学系，北京 100875
  • 收稿日期:1999-10-29 修回日期:2000-01-20 发布日期:2000-06-15
  • 通讯作者: 雷鸣

Theoretical Study on Some Elementary Reactions of the Olefin Hydroformylation Cycle Catalyzed by Carbonyl Cobalt

Lei Ming, Feng Wen-Lin, Xu Zhen-Feng   

  1. Department of Applied Chemistry,Beijing University of Chemical Technology,Beijing 100029|Department of Chemistry,Beijing Normal University,Beijing 100875
  • Received:1999-10-29 Revised:2000-01-20 Published:2000-06-15
  • Contact: Lei Ming

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摘要：

采用有效核势能近似(ECP)从头算方法, 在HF/LANL2DZ水平下研究了羰基钴催化的氢甲酰化反应循环中的羰基插入、H2 氧化加成和脱氢还原系列基元反应步骤的反应机理. 优化得到了反应基态势能面的中间体、过渡态和产物的几何构型. 计算了反应活化位垒,并对各过渡态进行了振动分析以确认. 理论计算结果表明,羰基插入、H2 氧化加成、脱氢还原的基元反应步骤的活化位垒分别为67.79、139.11和44.78kJ•mol-1.

关键词: 羟基钴, 氢甲酰化反应, 从头算, 赝势法

Abstract:

Ab initio method with effective core potential (ECP) approximation, has been employed to study the reaction mechanisms of some elementary reactions of the olefin hydroformylation cycle catalyzed by carbonyl cobalt at retricted Hartree Fock(RHF) level. The potential energy barriers for carbonyl insertion,H2 oxidative addition and reductive elimination are calculated as 67.79, 139.11 and 44.78 kJ•mol-1,respectively.The results indicate that the elementary reaction,H2 oxidative addition plays a more important role than carbonyl insertion and reductive elimination in olefin hydroformylation cycle catalyzed by carbonyl cobalt.

Key words: Carbonyl cobalt, Hydroformylation, Ab initio method, Effective core potential