Ab initio studies on the reagent Ph 3PCl 2

Abstract

We report ab initio calculations at the B3LYP/6-311G** level of theory for the title reagent. Four stationary points on the molecular potential energy surface have been located and characterized. Three of these stationary points are energy minima, one a saddle point. The minima correspond to the conventional Ph 3PCl 2 (three-fold Cl–P–Cl axis with twisted phenyl rings), the ion-pair [Ph 3PCl] +Cl − and a four-coordinated Ph 3PCl 2 spoke structure that can best be described as charge transfer on account of the substantial charge transfer from the Ph 3P fragment to Cl 2 (as measured by conventional Mulliken population analysis). The saddle point geometry is similar to the conventional three-fold Cl–P–Cl structure, but the phenyl groups are coplanar.