【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。更多还原

【Abstract】 The mechanism of cycloaddition reaction between singlet carbene and Formylchloride has been investigated by using ab initio MO theory of the restricted Hartree-Fock at HF/3-21G^* level.Geometry optimization,vibrational analysis and energies have been done for 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-free 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.更多还原