类锗烯H2C＝GeLiCl与RH(R=F,OH,NH2)的插入反应

Insertion Reactions of the Germylenoid H_2C=GeLiCl with RH(R=F, OH, NH_2)

采用DFTB3LYP和QCISD方法研究了不饱和类锗烯H2C!GeLiCl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!GeLiCl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173.53、194.48和209.05kJ·mol-1,反应热分别为60.18、72.93和75.34kJ·mol-1.相同条件下发生插入反应时,反应活性顺序都是H—F>H—OH>H—NH2.

The insertion reactions of the germylenoid H2C=GeLiCl with RH（R=F, OH, NH2） were studied using the DFF 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. The calculated results indicated that the mechanisms of the insertion reactions of H2C=GeLiCl with HF, H2O, and NH3 were 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 were 173.53, 194.48, and 209.05 kJ·mol^-1, and the reaction energies for the three reactions were 60.18, 72.93, and 75.34 kJ·mol^-1, respectively. Under the same situation, the insertion reactions should occur easily in the following order： H--F〉H---OH〉H--NH2,