双[1,2-二(三氟甲基)乙烯-1,2-二硫基]镍与丁二烯反应的溶剂效应

Solvent Effect in the Reaction between Bis[1,2-di(trifluoromethyl) ethylene-1,2-dithiolato] Nickel and Butadiene

采用密度泛函理论(DFT)在B3LYP/6-31G(d)水平上研究了双[1,2-二(三氟甲基)乙烯-1,2-二硫基]镍(Ni[S2C2(CF3)2]2)与丁二烯的反应机理.采用极化连续介质模型(PCM),考察了溶剂对各反应驻点的电荷分布、偶极矩、溶剂化自由能的影响.计算结果表明:Ni[S2C2(CF3)2]2与丁二烯的反应为前线轨道对称性匹配的协同反应,溶剂介电常数的增大有利于稳定各反应驻点.同时在同种溶剂中,过渡态和产物稳定的程度大于反应物,从而反应更加容易进行.

We studied the reaction mechanism for the reaction between bis[1,2-di（trifluoromethyl）ethylene-1,2-dithiolato] nickel （Ni[S2C2（CF3）2]2） and butadiene by density functional theory （DFT） at the B3LYP/6-31G（d） level. The solvent effect on the charge distribution, dipole moment, and solvation free energies of the stationary points were investigated using the polarizable continuum model （PCM）. The calculation results showed that this reaction was orbital symmetry allowed and concerted. The reaction stationary points become more stable with an increase of solvent dielectric constant. Additionally, the degree of stabilization for the transition state and the product is larger than that of the reactants in the same solvent, which means that the reaction occurs more easily.