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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,溶剂效应十分显著,而在ε>7.58时,溶剂效应的影响将达到极限.
Using density functional theory (DFT) at B3LYP / 6-31G (d) level, we calculated the molecular sites (reactants, intermediates, products and two transition states) on the potential surface of nickel dithiolene reacted with ethylene The influence of solvent on the reaction of nickel dithiolenes with ethylene was investigated by means of the geometrical configuration, charge distribution and some thermodynamic parameters. It was found that with the increase of solvent polarity, the bond between ethylene and nickel dithiolenes The energy difference between the frontier orbital of the two transition states increases and the energy difference between the frontier orbital of the product and the intermediate decreases while the solvent stability at each site also decreases.Furthermore, Can improve the stability of the product and is conducive to the reaction.Moreover, the solvent effect is very significant when the relative permittivity of solvent 1.00≤ε≤7.58, while the effect of solvent effect will reach the limit when ε> 7.58.