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Título: | Interplay of F-H ...F hydrogen bonds and P ...N pnicogen bonds |
Autor: | Del Bene, Janet E.; Alkorta, Ibon CSIC ORCID ; Sánchez-Sanz, Goar CSIC ORCID; Elguero, José CSIC ORCID | Fecha de publicación: | 2012 | Editor: | American Chemical Society | Citación: | The journal of physical chemistry, A, Molecules, spectroscopy, kinetics, environment & general theory 116: 9205- 9213 (2012) | Resumen: | Ab initio MP2/aug′-cc-pVTZ calculations have been carried out to investigate the influence of F-H•••F hydrogen bonds on the P•••N pnicogen bond in complexes nFH:(H 2FP:NFH 2) for n = 1-2, and a selected complex with n = 3. The NBO analysis indicates that the N(lp) → P-Fσ* charge-transfer transition has a much greater stabilizing effect than the P(lp) → N-Fσ* transition. When hydrogen bonding occurs at P-F, charge transfer associated with the pnicogen bond and the hydrogen bond are in the same direction but are in opposite directions when hydrogen bonding occurs at N-F. As a result, the formation of F-H•••F hydrogen bonds at P-F leads to shorter P•••N distances, increased strength of P•••N bonds, and synergistic energetic effects; hydrogen bonding at N-F has opposite effects. 31P and 15N chemical shieldings do not correlate with charges on P and N, respectively, but 31P shieldings correlate quadratically with the P-N distance. 1pJ(P-N) coupling constants do not correlate with the intermolecular P-N distance. However, when hydrogen bonding occurs only at P-F, 1pJ(P-N) decreases in absolute value as the P-N distance decreases, thereby approaching 1J(P-N) for H 2P-NH 2. However, the P•••N bond in 3FH:(H 2FP:NFH 2) has little covalent character, unlike the P•••P bond in the corresponding complex 3FH:(PH 2F) 2. © 2012 American Chemical Society. | URI: | http://hdl.handle.net/10261/63706 | DOI: | 10.1021/jp307083g | Identificadores: | doi: 10.1021/jp307083g issn: 1089-5639 e-issn: 1520-5215 |
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