H2XP:OH2 Complexes: Hydrogen vs. Pnicogen Bonds

A search of the Cambridge Structural Database (CSD) was carried out for phosphine-water and arsine-water complexes in which water is either the proton donor in hydrogen-bonded complexes, or the electron-pair donor in pnicogen-bonded complexes. The range of experimental P-O distances in the phosphine complexes is consistent with the results of ab initio MP2/aug’-cc-pVTZ calculations carried out on complexes H2XP:OH2, for X = NC, F, Cl, CN, OH, CCH, H, and CH3. Only hydrogen-bonded complexes are found on the H2(CH3)P:HOH and H3P:HOH potential surfaces, while only pnicogen-bonded complexes exist on H2(NC)P:OH2, H2FP:OH2, H2(CN)P:OH2, and H2(OH)P:OH2 surfaces. Both hydrogen-bonded and pnicogen-bonded complexes are found on the H2ClP:OH2 and H2(CCH)P:OH2 surfaces, with the pnicogen-bonded complexes more stable than the corresponding hydrogen-bonded complexes. The more electronegative substituents prefer to form pnicogen-bonded complexes, while the more electropositive substituents form hydrogen-bonded complexes. The H2XP:OH2 complexes are characterized in terms of their structures, binding energies, charge-transfer energies, and spin-spin coupling constants 2hJ(O-P), 1hJ(H-P), and 1J(O-H) across hydrogen bonds, and 1pJ(P-O) across pnicogen bonds