CuO＋氧化苯直接形成苯酚反应机理的理论研究  

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

作　　者：谢均[1] 李桂英[1] 胡常伟[1] 

机构地区：[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

出　　处：《高等学校化学学报》2011年第2期339-343,共5页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:20502017)资助

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,同时计算了单态和三态势能面.计算结果表明,苯与CuO+间相互作用主要为σ键,反馈π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.The mechanism of the oxidation of benzene to phenol by CuO＋ was investigated 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 σ coordination and bond,weakly back-donation π 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.

关 键 词：C—H键活化 苯羟基化 密度泛函理论 电荷分解分析 

分 类 号：O641[理学—物理化学]