Quantum-chemical study of chlorophosphoranes: I. Structure of the (C6H5)2PCl3 molecule in gaseous and crystalline states

Abstract

The quantum-chemical calculations of the (C6H5)2PCl3 molecule were performed by the methods RHF/6-31G(d) and MP2/6-31G(d) with complete and partial optimization of its geometry. The results of calculations were used for evaluating the NQR frequencies of 35Cl and the parameters of asymmetry of the of electric field gradient on the 35Cl nuclei of this molecule. According to the results of calculations with the partial optimization of geometry and to the experimental data of 35Cl NQR the bond lengths were found of central atom P in the solid state of this compound. The mutual influence of its axial and equatorial bonds was studied. It is shown that in chlorophosphoranes the 35Cl NQR frequencies of the axial and equatorial chlorine atoms decrease with the decrease in the bond lengths of phosphorus atom.