溶剂对镍连二硫烯与乙烯反应的影响

用密度泛函理论在B3LYP/6-31G(d)水平上计算得到了镍连二硫烯与乙烯反应的势能面上各驻点(反应物、中间体、产物和两个过渡态)的分子几何构型、电荷分布和一些热力学参数等，研究了溶剂对镍连二硫烯与乙烯反应的影响.结果发现，随着溶剂极性的增强，乙烯和镍连二硫烯之间的成键作用增强，两个过渡态的前线轨道能量差增大，而产物和中间体的前线轨道能量差却减小，同时各驻点的溶剂稳定化能也减小.进一步，这表明溶剂极性增强能提高产物的稳定性，有利于反应的进行.此外，当溶剂相对介电常数1.00≤ε≤7.58时

The solvent effects on the complexing reaction of nickel dithiolene and ethylene

Theoretical studies of solvent effects on the reaction of complexing ethylene and nickel dithiolene have been carried out by calculating the molecular geometry, electron distribution, and frequency of all the stagnation points existing in the reaction potential profiles by means of density functional theory methods at the B3LYP/6-31G(d) level. On the basis of frequency analysis and statistical thermodynamic theory, some thermodynamic parameters for the titled compound have been obtained for different solvents. It is shown that the bond energy of ethylene and nickel dithiolene enhances with the increase of the solvent polarity. In addition, the frontier orbital energy gaps of the two transition states will increase, while those of the product and the intermediate as well as the corresponding solvation stabilization energy will decrease. Furthermore, these results demonstrate that in polar solvents the reaction of complexing ethylene and nickel dithiolene may become easier and faster to occur and yield a more stable product. Notably, an obvious solvent effect can be observed when the value of the solvent dielectric constant lies between 1.0 and 7.58, while the solvent effect will tend to be maximal when the value of solvent dielectric constant exceeds 7.58.