高等学校化学学报

高等学校化学学报 ›› 2011, Vol. 32 ›› Issue (2): 339.

• 研究论文 • 上一篇    下一篇

CuO+氧化苯直接形成苯酚反应机理的理论研究

谢均,李桂英,胡常伟   

  1. 四川大学化学学院, 绿色化学与技术教育部重点实验室, 成都 610064
  • 收稿日期:2010-07-29 修回日期:2010-11-11 出版日期:2010-02-10 发布日期:2011-02-23
  • 通讯作者: 胡常伟 E-mail:gchem@scu.edu.cn
  • 基金资助:

    国家自然科学基金(批准号: 20502017)资助.

Theoretial Study on the Mechanism for Direction Oxidation of Benzene to Phenol by CuO+

XIE Jun, LI Gui-Ying, HU Chang-Wei*   

  1. Key Laboratory Green Chemistry and Technology, Ministry of Education College of Chemistry, Sichuan University,Chengdu 610064, China
  • Received:2010-07-29 Revised:2010-11-11 Online:2010-02-10 Published:2011-02-23
  • Contact: HU Chang-Wei E-mail:gchem@scu.edu.cn
  • Supported by:

    国家自然科学基金(批准号: 20502017)资助.

PDF (PC)

摘要： 在UB3LYP/6-31G(d,p) 水平下研究了CuO+氧化苯形成苯酚反应的详细机理，同时计算了单重态和三重态势能面。计算结果表明，苯与CuO+间相互作用主要为?配键，反馈?键较弱. CuO+氧化苯形成苯酚反应通过非自由基氢摘取机理完成，主要包括C-H键活化和苯基与羟基耦合两步反应. C-H键活化为整个反应的决速步骤. C-H键活化步骤涉及势能面交叉，且自旋交叉与动力学相关。CuO+氧化苯形成苯酚反应在气相中很容易进行.

Abstract: The mechanism of the oxidation of benzene to phenol by CuO+ was investigated in details at the UB3LYP/6-31G(d,p) level of theory. Both the singlet and triplet potential energy profiles were studied. The computational results indicate that the interaction between benzene and CuO+ is mainly the ? coordination and bond, weakly back-donation ? bond also contributes. The oxidation of benzene to phenol by CuO+ proceeds through the non-radical H-abstraction mechanism, which mainly includes the C-H bond activation and the coupling of phenyl and hydroxyl. The C-H bond activation is the rate-limiting step. The entrance channel of the C-H bond activation step involves the spin cross between the singlet and triplet potential energy profiles. The oxidation of benzene to phenol by CuO+ is predicted to occur easily in the gas phase.

TrendMD: