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...
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doaj-054f1bb1d73543d6b958ab74e1c71d432020-11-24T21:57:47ZengMDPI AGCrystals2073-43522016-02-01621910.3390/cryst6020019cryst6020019H2XP:OH2 Complexes: Hydrogen vs. Pnicogen BondsIbon Alkorta0Janet E. Del Bene1Jose Elguero2Instituto de Química Médica (CSIC), Juan de la Cierva, 3. E-28006 Madrid, SpainDepartment of Chemistry, Youngstown State University, Youngstown, OH 44555, USAInstituto de Química Médica (CSIC), Juan de la Cierva, 3. E-28006 Madrid, SpainA 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.http://www.mdpi.com/2073-4352/6/2/19hydrogen bondspnicogen bondsCSDab initio calculationsstructures and binding energiescharge-transfer energiesEOM-CCSD spin-spin coupling constants |
collection |
DOAJ |
language |
English |
format |
Article |
sources |
DOAJ |
author |
Ibon Alkorta Janet E. Del Bene Jose Elguero |
spellingShingle |
Ibon Alkorta Janet E. Del Bene Jose Elguero H2XP:OH2 Complexes: Hydrogen vs. Pnicogen Bonds Crystals hydrogen bonds pnicogen bonds CSD ab initio calculations structures and binding energies charge-transfer energies EOM-CCSD spin-spin coupling constants |
author_facet |
Ibon Alkorta Janet E. Del Bene Jose Elguero |
author_sort |
Ibon Alkorta |
title |
H2XP:OH2 Complexes: Hydrogen vs. Pnicogen Bonds |
title_short |
H2XP:OH2 Complexes: Hydrogen vs. Pnicogen Bonds |
title_full |
H2XP:OH2 Complexes: Hydrogen vs. Pnicogen Bonds |
title_fullStr |
H2XP:OH2 Complexes: Hydrogen vs. Pnicogen Bonds |
title_full_unstemmed |
H2XP:OH2 Complexes: Hydrogen vs. Pnicogen Bonds |
title_sort |
h2xp:oh2 complexes: hydrogen vs. pnicogen bonds |
publisher |
MDPI AG |
series |
Crystals |
issn |
2073-4352 |
publishDate |
2016-02-01 |
description |
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. |
topic |
hydrogen bonds pnicogen bonds CSD ab initio calculations structures and binding energies charge-transfer energies EOM-CCSD spin-spin coupling constants |
url |
http://www.mdpi.com/2073-4352/6/2/19 |
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