Pnicogen-pnicogen bonded complexes formed between PO2X (X = H, CN and F) as the Lewis acids and a series of phosphorous bases PH2Y (Y=H, OH, OCH3, CH3 and NH2) are investigated by means of MP2 and M06-2X computational methods. Interaction energies of these complexes are in the range of -11 to -45 kcal/mol at the MP2/aug-cc-pVTZ level. Complexation of PO2X with the PH2Y leads to P...P bonds with a significant degree of covalency. The spin-spin coupling constant across P...P interaction depends on the nature of X and Y substituents. Fermi-contact (FC) term is an excellent approximation to total (ip)j(p-p). (C) 2015 Elsevier B.V. All rights reserved.