On the electronic structure of dihalogenophosphenium cations

Abstract

The bonding properties of the dihalogenophosphenium cations, PX 2 (+), X = F, Cl, Br, I, are evaluated by relativistic effective core potential calculations with a DZP basis set. Our investigations include an analysis of the singlet-triplet energy separation in the cations and the determination of the relative cation and anion stabilities in the gas phase, via corresponding group transfer reactions. A comparison is made with other stabilized, previously reported low-coordinated π-bonded phosphorus cations.