New insights into the insertion reactions of germylenoid H2GeLiF with RH (R=F, OH, NH2)

作者：Yan, Bingfei; Li, Wenzuo^*; Xiao, Cuiping; Liu, Zhenbo; Li, Qingzhong; Cheng, Jianbo

来源：Journal of Molecular Modeling, 2015, 21(4): 68.

DOI：10.1007/s00894-015-2626-0

• H2GeLiF
• RH (R=F, OH, NH2)
• Insertion reaction
• B3LYP
• QCISD

In the present work, a new pathway of the insertion reactions of H2GeLiF with RH (R=F, OH, NH2) was investigated using DFT B3LYP and QCISD methods. The geometries of the stationary points on the potential energy surfaces in the reactions were optimized at the B3LYP/6-311+G (d, p) level and then the single-point energies were calculated at the QCISD/6-311++G (d, p) level. The calculated results indicated that the initial step of all the reactions is the isomerization of the p-complex structure to a three-membered-ring structure. After isomerization, the insertion reactions of three-membered-ring H2GeLiF with RH (R=F, OH, NH2) take place. The QCISD/6-311++G (d, p)//B3LYP/6-311+G (d, p) calculated potential energy barriers of the three reactions were 89.77, 137.40, and 167.45 kJ mol(-1), respectively. Under the same situation, the insertion reactions should occur easily in the following order H-F>H-OH>H-NH2. Compared with the direct insertion reactions of H2GeLiF with RH (R=F, OH, NH2), the two-step insertions have lower activation barriers and should be more favorable.

• 出版日期2015-4
• 单位烟台大学