Electronic properties of tricoordinated phosphorus in hexagonal phosphininium compounds and molecular aromaticity.

Calculations with B3LYP within quantum chemical density functional theory have been carried out for 1-H-phosphininium cation and a series of 1-R-phosphininium molecules (R = cyclopentadiene, α and β pyrroles, α and β phosphole, C5BH5&bond; and CH2&bond;). The negative nuclear-independent chemical shift values and the positive aromatic stabilization energies confirm that they are aromatic compounds. In particular, the 1-H-phosphininium cation even exhibits stronger aromatic character than the well-known aromatic phosphinine. The aromatic substituents have strong capability to attract electrons. It is the conjugation and aromaticity that keeps the stability and conformations of the molecules investigated. Owing to the perturbation of the aromatic substituted groups, the predicted large T values and the enlarged HOMO-LUMO gap of the phosphininium cation indicate that these compounds are expected in experiment. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2007 [ABSTRACT FROM AUTHOR]