铁催化芳香酮芳环碳氢键和烯烃加成反应机理的理论研究  

Theoretical Studies on the Mechanism Iron-Catalyzed Addition of C-H Bonds in Aromatic Ketones to Alkenes

作　　者：李乐乐 王智香 申珊珊 王旭 闫睿魁[1,2] Li Lele;Wang Zhixiang;Shen Shanshan;Wang Xu;Yan Ruikui(College of Chemistry and Chemical Engineering,Shaanxi Key Laboratory of Chemical Reaction Engineering,Yan’an University,Yan’an 716000,China;Key Laboratory of New Energy&New Functional Materials,Yan’an University,Yan’an 716000,China)

机构地区：[1]延安大学化学与化工学院陕西省化学反应工程重点实验室,陕西延安716000 [2]延安大学新功能新材料实验室,陕西延安716000

出　　处：《山东化工》2022年第7期37-39,共3页Shandong Chemical Industry

基　　金：陕西省自然科学基础研究计划项目(2020JQ-793);延安大学项目(YDQ2019-19,YDBK2019-34);大创项目(D2019030)。

摘　　要：采用ub3pw91方法研究了铁催化芳香酮芳环碳氢键和烯烃的加成反应机理。计算得到了反应过程中所有物种的几何结构和频率,构建了该反应势能面。研究结果表明,铁催化芳香酮芳环碳氢键和烯烃加成反应通过氧化加成、氢原子转移和还原消除三个步骤完成。其中,铁催化剂对芳香酮芳环碳氢键氧化加成为该反应的决速步骤,对应活化能为22.5 kcal/mol,总反应放热12.7 kcal/mol。计算结果与实验结果定性一致。Reaction mechanism of iron catalyzed addition reaction between aromatic ketones and olefins was investigated at the level of ub3pw91.The geometry and frequency of all species in the reaction process were calculated,and the potential energy surface of the reaction was constructed.The results show that the iron catalyzed hydrogenation of aromatic ketones and alkenes is accomplished by three steps:oxidation addition,hydrogen atom transfer and reduction elimination.Among them,the oxidation of aromatic ketones by iron catalyst is the rate-determining step of the reaction,the corresponding activation energy is 22.5 kcal/mol,and the total exothermic reaction is 12.7 kcal/mol.The calculated results are qualitatively consistent with the experimental results.

关 键 词：铁催化 芳香酮 烯烃 反应机理 

分 类 号：O641.12[理学—物理化学]