Quantum-chemical study of chlorophosphoranes: III. Structure of the molecules of the series (X,X′) a P(Cl3) e . Mutual influence of axial and equatorial substituents

Abstract

Quantum-chemical calculations by the methods RHF/6-31G(d) and MR2/6-31G(d) of a series of chlorophosphoranes (X,X′)aP(Cl3)e with complete optimization of their geometry were performed. The results of the calculations were used to estimate 35Cl NQR frequencies and asymmetry parameters of the electric field gradient at the 35Cl nuclei of these molecules. From the results of calculations using RHF/6-31G(d) method with partial geometry optimization and experimental data on 35Cl NQR the lengths of the bonds of central P atom of the compounds in solid state were found. Mutual influence of axial and equatorial substituents was revealed. As in other chlorophosphoranes, the decrease in the length of axial or equatorial P-Cl bonds leads to the decrease in NQR frequencies of axial and equatorial chlorine atoms, respectively.