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Título

Phosphorus as a simultaneous electron-pair acceptor in intermolecular P⋯N pnicogen bonds and electron-pair donor to lewis acids

Autor Del Bene, Janet E.; Alkorta, Ibon ; Sánchez-Sanz, Goar; Elguero, José
Fecha de publicación 2013
EditorAmerican Chemical Society
Citación The journal of physical chemistry, A, Molecules, spectroscopy, kinetics, environment & general theory 117: 3133- 3141 (2013)
ResumenAb initio MP2/aug'-cc-pVTZ calculations have been performed to investigate the structures and energies of binary complexes LA:PH2F and LA:PH3 and of ternary complexes LA:H2FP:NFH2 and LA:H3P:NH3 in which the pnicogen-bonded P atom also acts as an electron-pair donor to a Lewis acid (LA), for LA = BH3, NCH, ClH, FH, FCl, and HLi. Hydrogen bonds, halogen bonds, and dative covalent bonds are found at P in some cases, depending on the nature of the Lewis acid. HLi forms a lithium bond with P only in the binary complex HLi:PH3. The binding energies of ternary complexes exhibit a classical synergistic effect, although the computed cooperativity may be overestimated due to neglect of the interaction of the Lewis acid with NH2F or NH3 in some cases. The hydrogen-bonding Lewis acids appear to have little effect on the strength of the P⋯N bond, while the remaining Lewis acids strengthen the pnicogen bond. 31P absolute chemical shieldings increase in LA:H2FP:NFH2 complexes relative to the corresponding LA:PH2F complexes as the positive charge on P decreases, while chemical shieldings decrease in LA:H3P:NH3 relative to the corresponding LA:PH3 complexes as the positive charge increases. Absolute values of 1pJ(P-N) spin-spin coupling constants in complexes LA:H2FP:NFH2 decrease as the P-N distance decreases. It appears that this behavior is associated with the presence of a second intermolecular interaction, whether electron-donation by P or hydrogen bond formation at P-F.
URI http://hdl.handle.net/10261/101451
DOI10.1021/jp401480y
Identificadoresdoi: 10.1021/jp401480y
issn: 1089-5639
e-issn: 1520-5215
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