ON THE ELECTRONIC-STRUCTURE OF DIHALOGENOPHOSPHENIUM CATIONS

The bonding properties of the dihalogenophosphenium cations, PX2(+), X = F, Cl, Br, I, are evaluated by relativistic effective core potentia l calculations with a DZP basis set. Our investigations include an ana lysis 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 mad e with other stabilized, previously reported low-coordinated pi-bonded phosphorus cations. (C) 1998 Elsevier Science B.V.