单重态卡宾与甲酰氯环加成反应机理的理论研究  

Theoretical Study on the Mechanism of the Cycloaddition Reaction between Carbene and Formyl chloride

作　　者：武卫荣[1] 于海彬[2] 卢秀慧[2] 

机构地区：[1]济宁师范专科学校化学系,山东济宁272000 [2]济南大学化学化工学院,山东济南250022

出　　处：《济宁师范专科学校学报》2006年第3期10-12,共3页Journal of Jining Teachers College

摘　　要：用限制的H artree-Fock从头算分子轨道理论研究了单重态卡宾与甲酰氯环加成反应的机理。在HF/3-21G*基组水平上,计算了反应势能面上各驻点的构型参数、振动频率和能量。计算结果表明,该反应的主反应途径由两步组成:首先,两反应物通过一无势垒的放热反应生成一富能中间体INT a,放出的热量为36.47 kJ.m o-l 1;然后该中间体经过渡态TSa异构化为一三元环产物P,其势垒为23.22 kJ.m o-l 1。该反应途径与其竞争反应途径相比具有很好的选择性。The mechanism of cycloaddition reaction between singlet carbene and Formylchloride has been investigated by using ab initio UO theory o~ the restricted Hartree-Fock at HF/3-21G^＊ level. Geometry optimization, vibrational analysis and energies have been done lor the involved stationary points on the potential energy surface . The results show that this reaction proceeds via two steps： （ Ⅰ ）Two reactants firstly form inermediate （INTa） through a energy-lree barrier exotheromal reaction of 36.47 kJ·mol^-1 （ Ⅱ） INTa isomerizes to the three - membered product （P） via a transition state （TSa）, in which the energy barrier is 23.22 kJ·mol^-1. Compared with its competitive reaction paths, this channel has an excellent selectivity.

关 键 词：卡宾 甲酰氯 环加成反应 HF理论 

分 类 号：O641[理学—物理化学]