【摘要】 采用DFTB3LYP和QCISD方法研究了类硅烯H2C=SiLiBr与RH(R=F,OH,NH2)的插入反应.在B3LYP/6-311+G(d,p)水平上优化了反应势能面上的驻点构型.结果表明,H2C=SiLiBr与HF,H2O或NH3发生插入反应的机理相同.QCISD/6-311++G(d,p)//B3LYP/6-311+G(d,p)计算的三个反应的势垒分别为148.62,164.42和165.07kJ·mol-1,反应热分别为-69.63,-43.02和-28.27kJ·mol-1.相同条件下发生插入反应时,反应活性都是H—F>H—OH>H—NH2.更多还原

【Abstract】 The insertion reactions of the silylenoid H2C=SiLiBr to RH(R=F,OH,NH2) were studied by using the DFT B3LYP and QCISD methods.The geometries of the stationary points on the potential energy surfaces of the reactions were optimized at the B3LYP/6-311+G(d,p) level of theory.The calculated results indicate that the mechanisms of the insertion reactions of H2C=SiLiBr to HF,H2O,and NH3 are identical to each other.The QCISD/6-311++G(d,p)//B3LYP/6-311+G(d,p) calculated potential energy barriers of the three reactions are 148.62,164.42,and 165.07 kJ/mol,and the reaction energies for the three reactions are -69.63,-43.02,and -28.27 kJ/mol,respectively.Under the same situation,the insertion reactions should occur easily in the following order H—F>H—OH>H—NH2.更多还原