锡烯与一些亲核试剂加成反应的理论研究

Theoretical Study on the Addition Reactions between Stannenes and Some Nucleophilic Reagents

采用密度泛函理论(DFT)方法研究了锡烯与一些亲核试剂(H_2O、MeOH及PhOH)间的加成反应的微观机理和势能剖面,考察了Sn=C双键中Sn原子和C原子上的取代基对反应势能剖面的影响.计算结果表明,H_2O及MeOH的单聚体、二聚体及三聚体均可作为亲核试剂与锡烯发生加成反应,但只有PhOH的单聚体才能与锡烯发生加成反应.Sn=C双键中Sn原子上的吸电子基团和给电子基团分别能使加成反应的活化Gibbs自由能降低或升高,而C原子上的取代基则有相反的效应.所涉及的三种亲核试剂的反应活性从高到低的顺序为:MeOH>H_2O>PhOH.

Density functional theory（DFT）calculations were performed to study the mechanism and potential energy surface of the addition reactions between stannenes and some nucleophilic reagents（H_2O,MeOH and PhOH）,and the influence of substituents at Sn or C atoms of Sn=C double bond on the potential energy surface was investigated.The results demonstrated that the monomer,dimer or trimer of H_2O or MeOH may behave as nucleophilic reagent toward stannenes,while only the monomer of PhOH can react with stannenes.The electron-withdrawing or electron-donating groups at Sn atom of Sn=C double bond can lower or elevate the Gibbs free energies of activation,respectively.However,the effects of substituents at C atom are just the reverse.The addition reactivity of three nucleophilic reagents involves in this research arranges as follows：MeOH H_2O PhOH.