Theoretical investigation on the insertion reactions of the germylenoid H2GeLiF with RH (R = Cl, SH, PH2)

The insertion reactions of the germylenoid H2GeLiF with RH (R = Cl, SH, PH2) were studied for the first time 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 indicated that the mechanisms of the insertion reactions of H2GeLiF with HCl, H2S, and PH3 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 81.80, 123.39 and 205.56 kJ/mol, and the reaction energies for the three reactions are -58.74, -33.51 and -13.35 kJ/mol, respectively. Under the same situation, the insertion reactions should occur easily in the following order H - Cl > H - SH > H - PH2. The insertion reaction in THF solution is easier than in gas phase.