铜类卡宾催化乙烯环丙烷化反应途径的密度泛函研究  

Studies on Cyclopropanation Reaction Pathways of Ethylene Catalyzed by Copper Carbenoid with Density Function

作　　者：张兴辉[1] 耿志远[2] 王永成[2] 方冉[2] 王冬梅[2] 戴国梁[2] 吕玲玲[2] 赵存元[2] 

机构地区：[1]甘肃联合大学化工学院,甘肃兰州730000 [2]西北师范大学化学化工学院,甘肃兰州730070

出　　处：《宁夏大学学报（自然科学版）》2006年第3期237-242,共6页Journal of Ningxia University(Natural Science Edition)

基　　金：甘肃省教育厅基金资助项目(021-22)

摘　　要：运用密度泛函B3LYP方法研究了过渡金属铜类卡宾与乙烯的环丙烷化反应机理,对3种不同铜的SS试剂CH3CuCHCl2,ClCuCH2Cl及CH3CuCHI2分别与CH2CH2反应的各反应物、中间体、过渡态、产物构型的全部结构几何参数进行了优化,用内禀反应坐标(IRC)计算和频率分析法,对过渡态进行了确定和验证.结果表明,CH3CuCHCl2和CH3CuCHI2与CH2CH2环丙烷化反应按亚甲基转移机理和卡宾金属化机理都可以进行,与锂类卡宾的反应机理相同,而ClCuCH2Cl与CH2CH2环丙烷化反应则更容易按卡宾金属化机理进行.The cyclopropanation reaction of ethylene with copper carbenoid LSimmons-Smith（SS）reagent] are stualea by B3LYP hybrid density functional method. The geometries for reactants, the transition states and the products are completely optimized. All of the transition states are verified by the vibrational analysis and the intrinsic reaction coordinate （IRC） calculations. The results show that both CH3 CuCHCl2 and CH3CuCHI2 react with ethylene are fast via the methylene transfer pathway and carbometalation pathway, and both processes are fast for the lithium carbenoid, but the reaction barriers for cyclopropanation of ethylene with ClCuCH2Cl become lower via carbometalation pathway than methylene transfer pathway.

关 键 词：铜类卡宾 环丙烷化 Simmons—Smith反应 密度泛函方法 

分 类 号：O641[理学—物理化学]