Yan Bingfei, Li Wenzuo, Xiao Cuiping, Liu Zhenbo, Li Qingzhong, Cheng Jianbo
The Laboratory of Theoretical and Computational Chemistry, College of Chemistry and Chemical Engineering Yantai University, Yantai, 264005, People's Republic of China.
J Mol Model. 2015 Apr;21(4):68. doi: 10.1007/s00894-015-2626-0. Epub 2015 Mar 7.
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.
在本工作中，使用密度泛函理论（DFT）的B3LYP和二次组态相互作用（QCISD）方法研究了H2GeLiF与RH（R = F、OH、NH2）插入反应的新途径。反应势能面上驻点的几何结构在B3LYP/6-311 + G(d, p)水平上进行了优化，然后在QCISD/6-311++G(d, p)水平上计算了单点能量。计算结果表明，所有反应的初始步骤都是p-络合物结构异构化为三元环结构。异构化后，三元环H2GeLiF与RH（R = F、OH）发生插入反应。这三个反应在QCISD/6-311++G(d, p)//B3LYP/6-311 + G(d, p)水平下计算得到的势能垒分别为89.77、137.40和167.45 kJ mol(-1)。在相同情况下，插入反应按以下顺序容易发生：H-F＞H-OH＞H-NH2。与H2GeLiF与RH（R = F、OH、NH2）的直接插入反应相比，两步插入具有较低的活化能垒，应该更有利。
