Ab initio studies on the reagent Ph3PCl2

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 Ph3PCl2 (three-fold Cl-P-Cl axis with twisted phenyl rings), the ion-pair [Ph3PCl]Cl-+(-) and a four-coordinated Ph3PCl2 spoke structure that can best be described as charge transfer on account of the substantial charge transfer from the Ph3P 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. (c) 2005 Elsevier B.V. All rights reserved.