物理化学学报 >> 1998, Vol. 14 >> Issue (09): 784-788.doi: 10.3866/PKU.WHXB19980904

研究论文 上一篇    下一篇

二氯卡宾与甲醛环加成反应的理论研究

卢秀慧, 王沂轩, 邓从豪   

  1. 济南大学化学系，济南 250002|山东大学化学院，济南 250100
  • 收稿日期:1997-12-08 修回日期:1998-01-24 发布日期:1998-09-15
  • 通讯作者: 卢秀慧

Theoretical Study on the Cycloaddition Reaction of Dichlorocarbene and Formaldehyde

Lu Xiu-Hui, Wang Yi-Xuan, Deng Cong-Hao   

  1. Chemistry Department,Jinan University,Jinan 250002|Institute of Chemsity of Shandong University,Jinan 250100
  • Received:1997-12-08 Revised:1998-01-24 Published:1998-09-15
  • Contact: Lu Xiu-Hui

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摘要：

用从头算方法研究了单重态二氯卡宾与甲醛的环加成反应，找到了反应的中间配合物和过渡态，讨论了反应机理，发现该反应分两步进行，第一步生成中间配合物，第二步是中间配合物异构化为产物──二氯环氧丙烷．在从头算的基础上，用统计效力学方法和过渡态理论计算了该反应的热力学函数和动力学性质，并作了讨论．

关键词: 卤代卡宾, 环加成反应, 从头算, 热力学和动力学性质

Abstract:

The cycloaddition reaction of singlet dichlorocarbene and formaldehyde has been studied by using ab initio method. The intermediate complex and transition state of this reaction have been optimized. The mechanism of the reaction has been discussed. It is found that in this reaction a complex is formed first from the reactants and then the complex isomerized to the product. The thermodynamic and kinetic properties of the reaction have been calculated with statistical thermodynamics and transition-state theory(TST) based on the ah initio level and the results have been discussed.

Key words: Halocarbene, Cycloaddition reaction, Ab initio calculation, Thermodynamic and kinetic properties