Ab initio calculations have been carried out in a systematic investigation of P···N pnicogen complexes H(2)XP:NXH(2) for X ═ H, CH(3), NH(2), OH, F, and Cl, as well as selected complexes with different substituents X bonded to P and N. Binding energies for complexes H(2)XP:NXH(2) range from 8 to 27 kJ mol(-1) and increase to 39 kJ mol(-1) for H(2)FP:N(CH(3))H(2). Equilibrium structures have a nearly linear A-P-N arrangement, with A being the atom directly bonded to P. Binding energies correlate with intermolecular N-P distances as well as with bonding parameters obtained from AIM and SAPT analyses. Complexation increases (31)P chemical shieldings in complexes with binding energies greater than 19 kJ mol(-1). One-bond spin-spin coupling constants (1p)J(N-P) across the pnicogen interaction exhibit a quadratic dependence on the N-P distance for complexes H(2)XP:NXH(2), similar to the dependence of (2h)J(X-Y) on the X-Y distance for complexes with X-H···Y hydrogen bonds. However, when the mixed complexes H(2)XP:NX'H(2) are included, the curvature of the trendline changes and the good correlation between (1p)J(N-P) and the N-P distance is lost.