二氟锗烯与乙烯环加成反应的机理

摘要

用二阶微扰和密度泛函理论研究单重态F2C＝Ge:与C2H4环加成反应机理,采用MP2/6-31G·和B3LYP/6-31G·方法计算势能面上驻点的构型参数、振动频率和零点能;利用CCSD(T)//MP2/6-31G·和CCSD(T)//B3LYP/6-31G·计算各构型的能量;利用CCSD(T)//MP2得到单线态F2C＝Ge:与C2H4环加成反应的势能面,在常温常压下,单线态F2C＝Ge:与C2H4的环加成无势垒放热反应生成三元环中间体INT,放出能量为29.5 kJ·mol-1.%The law of cyclic addition between singlet difluorogermylene and ethylene has been investigated with MP2/6-31G* and B3LYP/6-31G* methods, including geometry optimization, vibration analysis and zero-point energy for the involved stationary points on the potential energy surface.Energies for the involved configurations are calculated by CCSD(T)//MP2/6-31G* and CCSD(T)//B3LYP/6-31 G* methods ,respectively.On the basis of the surface energy profile obtained with CCSD (T)//MP2/6-31G * method for the cyclic addition between singlet difluorogermylene and ethylene, it can be predicted that cyclic addition between singlet difluorogermylene and ethylene is a barrier-free exothermic reaction of 29.5 k J/mol of a three-member ring intermediate INT.