二氯卡宾与异硫氰酸反应机理的量子化学研究  

Theoretical Study of Mechanism for the Carbon Dichlorine With Isothiocyanic Acid Reaction

作　　者：孔超[1] 韩彦霞[1] 陈东平[1] 高立国[2] 耿志远[3] 胡中爱[3] 

机构地区：[1]陇东学院化学化工学院,甘肃庆阳745000 [2]榆林学院化学与化工学院,陕西榆林719000 [3]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）》2012年第1期50-54,共5页Journal of Ningxia University(Natural Science Edition)

基　　金：国家自然科学基金资助项目(21163017);陇东学院青年科技创新基金资助项目(XYZK0716)

摘　　要：用密度泛函理论B3LYP方法研究了单、三重态CCl2与HNCS的反应机理.在B3LYP/6-311++G**水平上对反应物、中间体和过渡态进行了全几何参数优化;通过频率分析和内禀反应坐标(IRC)方法确认了中间体和过渡态;并用CCSD(T)/6-311++G**//B3LYP/6-311++G**方法计算了各个驻点的单点能.结果表明,对于单、三重态CCl2与HNCS反应,共有4条可行的反应通道,且通道CCl2(S)+HNCS→IM1→TS1→IM2→HCN+CCl2S(P1)反应能垒最低,为该反应的主反应通道;单重态抽提亚氨基通道反应能垒也比较低,为主反应通道的竞争通道.可为进一步实验研究提供参考.The reaction mechanism of singlet and triplet CCl2 with HNCS has been investigated by B3LYP method of density function theory.The geometries and harmonic of reactants,intermediates,transition states and products have been calculated at B3LYP/6-311＋ ＋G＊＊ level.Intermediates and transition states were confirmed by the results of vibration analysis and the IRC calculation.The energies of stationary point were calculated at CCSD（T）/6-311＋ ＋G＊＊ / /B3LYP/6-311＋ ＋G＊＊ level.Four feasible reaction pathways were investigated in this study.Analysis indicated that the reaction CCl2（S）＋HNCS→IM1→TS1→IM2→HCN＋ CCl2S（P1） were the main pathways,the activation energy of which was the lowest.In the reaction system,the activation energy of the singlet NH Abstraction pathway is not very high,and it was the competitive reaction pathway.

关 键 词：二氯卡宾 异硫氰酸 反应机理 活化能 过渡态 

分 类 号：O641[理学—物理化学]