Zhang Mingxia, Li Wenzuo, Li Qingzhong, Cheng Jianbo
College of Chemistry and Chemical Engineering, Yantai University, Yantai, 264005, People's Republic of China.
J Mol Model. 2017 Jul;23(7):199. doi: 10.1007/s00894-017-3375-z. Epub 2017 Jun 7.
Theoretical calculations using the M062X and QCISD methods were performed on the addition reactions of the aluminum germylenoid HGeAlCl with ethylene. The most two stable structures of germylenoid HGeAlCl, i.e., the p-complex and three-membered ring structures, respectively, were employed as reactants. The calculated results indicate that, for the p-complex, HGeAlCl there are two pathways, I and II, of which path I involves just one transition state, while path II involves two transition states between reactants and products. Comparing the reaction barrier heights of path I (44.6 kJ mol) and II (37.6 kJ mol), the two pathways are competitive, with similar barriers under the same conditions, while for the three-membered ring structure, another two pathways, III and IV, also exist. Path III has one transition state; however, in path IV, two transition states exist. By comparing their barrier heights, path III (barrier height 39.2 kJ mol) could occur more easily than path IV (barrier height 92.8 kJ mol). Considering solvent effects on these addition reactions, the PCM model and CHCl solvent were used in calculations, and the calculated results demonstrate that CHCl solvent is unfavorable for the reactions, except for path II. In CHCl solvent, paths II and III are more favorable than paths I and IV.
使用M062X和QCISD方法对铝锗烯类化合物HGeAlCl与乙烯的加成反应进行了理论计算。分别采用锗烯类化合物HGeAlCl最稳定的两种结构，即π-络合物和三元环结构作为反应物。计算结果表明，对于π-络合物HGeAlCl，有I和II两条反应途径，其中途径I只涉及一个过渡态，而途径II在反应物和产物之间涉及两个过渡态。比较途径I（44.6 kJ/mol）和途径II（37.6 kJ/mol）的反应势垒高度，在相同条件下，这两条途径具有竞争性，势垒相似；而对于三元环结构，还存在另外两条途径III和IV。途径III有一个过渡态；然而，在途径IV中存在两个过渡态。通过比较它们的势垒高度，途径III（势垒高度39.2 kJ/mol）比途径IV（势垒高度92.8 kJ/mol）更容易发生。考虑到溶剂对这些加成反应的影响，计算中使用了PCM模型和CHCl溶剂，计算结果表明，除途径II外，CHCl溶剂对反应不利。在CHCl溶剂中，途径II和III比途径I和IV更有利。
