Features of the molecular structure of compounds of (Cl3PNAr)2 series (Ar = C6H4Z, Z = H, Cl) by quantum-chemical calculations and the data of 35Cl nuclear quadrupole resonance

Abstract

A series of dimeric molecules (Cl3PNAr)2 where Ar = C6H4Z, Z = H or Cl in 2–4 positions, was calculated by the RHF/6-31G* method with the full geometry optimization. A specific nature of the intramolecular steric orientation of aryl groups was revealed, therewith in the case Ar = C6H4Cl-2 short nonvalent contacts were founf between the ortho-chlorine atom and PCl3 group manifested in the peculiarity of geometric parameters and NQR spectroscopy data of this compound. The correlation of the 35Cl NQR frequencies of P-Cl bonds with the values of the charges on the chlorine atoms obtained by quantum-chemical calculations of the molecules was analyzed.