PUB - Publikationen an der Universität Bielefeld

Relative cation and anion stabilities of a selected variety of low-coordinated pi-bonded phosphorus compounds are evaluated for the gas phase by means of group transfer reactions at an ab initio RHF/SCF level with inclusion of electron correlation treatment (MP4SDTQ(fc)/6-31+g(d)). The cation stabilities reveal large variations; the largest cation stabilities are possessed by the diaminophosphenium cation and the phosphanetriylammonium cation. Interestingly the diphosphinophosphenium structure is capable of strong stabilization of the corresponding cation as well as the anion. An analysis of the frontier orbitals indicates that the cationic species can be divided into classes of structures, isolobal with a carbene or a cyanide, isocyanide, rsp.