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Crystals 2016, 6(2), 19; doi:10.3390/cryst6020019

H2XP:OH2 Complexes: Hydrogen vs. Pnicogen Bonds

1
Instituto de Química Médica (CSIC), Juan de la Cierva, 3. E-28006 Madrid, Spain
2
Department of Chemistry, Youngstown State University, Youngstown, OH 44555, USA
*
Authors to whom correspondence should be addressed.
Academic Editor: Sławomir Grabowski
Received: 6 January 2016 / Revised: 25 January 2016 / Accepted: 28 January 2016 / Published: 2 February 2016
(This article belongs to the Special Issue Analysis of Hydrogen Bonds in Crystals)
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Abstract

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. View Full-Text
Keywords: hydrogen bonds; pnicogen bonds; CSD; ab initio calculations; structures and binding energies; charge-transfer energies; EOM-CCSD spin-spin coupling constants hydrogen bonds; pnicogen bonds; CSD; ab initio calculations; structures and binding energies; charge-transfer energies; EOM-CCSD spin-spin coupling constants
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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MDPI and ACS Style

Alkorta, I.; Del Bene, J.E.; Elguero, J. H2XP:OH2 Complexes: Hydrogen vs. Pnicogen Bonds. Crystals 2016, 6, 19.

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