Quantum-chemical study of chlorophosphoranes: II. Structure of molecules of (Cl2) a P(Cl n X3−n ) e series, and mutual influence of axial and equatorial substituents

Abstract

The quantum-chemical calculations by the methods RHF/6-31G(d) and MP2/6-31G(d) of chlorophosphoranes of a series (Cl2)aP(ClnX3−n)e with complete and partial optimization of their geometry were performed. The results of calculations were used for evaluation of the frequencies of 35Cl NQR and the asymmetry parameters of the electric field gradient on the 35Cl nuclei of these molecules. According to the results of calculations with the partial geometry optimization and the experimental data on 35Cl NQR the bond lengths of central atom P in the solid state of the corresponding compounds were used. A substantial change in the NQR frequencies of the axial chlorine atoms and a weak change in the frequencies of the equatorial ones at a change in the number of the latter was explained.