硫原子上亲核取代反应的密度泛函理论研究

DFT Study of Nucleophilic Substitution at Sulfur

在B3LYP/6 3 11+G( 2df,p)的水平上 ,对反应X-+CH3 SCl (X =F ,Cl,Br,I)进行了理论研究 .计算结果表明 :X-(X =Cl,Br ,I)与CH3 SCl作用时 ,实际发生的是在硫原子上而不是在碳原子上的亲核取代反应 ,而且属于加成 -消去机理 .但是F-与CH3

A series of reactions, X- + CH3SCl (X = F, Cl, Br, I), were examined at B3LYP/6-311 + G(2df, p) level. Computational results indicate that X- (X = Cl, Br, 1) attacks preferably sulfur atom instead of carbon atom of CH3SCL The substitution reactions follow an addition-elimination mechanism. However, deprotonation reaction is much more favorable than substitution for reaction F- + CH3SCl.