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Carbenes as Electron-Pair Donors for P⋅⋅⋅C Pnicogen Bonds

AutorDel Bene, Janet E.; Alkorta, Ibon ; Elguero, José
Palabras claveCharge transfer
Covalent bonds
Noncovalent interactions
Carbenes
Hydrogen bonds
Fecha de publicación2017
EditorJohn Wiley & Sons
CitaciónChemphyschem
ResumenAb initio MP2/aug′-cc-pVTZ calculations were performed on the P⋅⋅⋅C pnicogen-bonded complexes of the singlet carbene molecules C(NH), C(OH), and cyclic C(OCH) [OHC] with HXP molecules, with X=F, Cl, NC, OH, CH, CN, CCH, and H. The HXP:C(NH) and HXP:C(OH) complexes have C symmetry and two different structures: one in which the symmetry plane of the complex and the local symmetry plane of the carbene are non-coplanar, and the other in which they are coplanar. The non-coplanar HXP:C(NH) and HXP:C(OH) complexes arise only when X is one of the more electronegative substituents. Coplanar HXP:C(NH) complexes form when X is one of the more electropositive substituents, whereas coplanar HXP:C(OH) complexes exist for all X. HXP:C(NH) and HXP:C(OH) are stabilized by covalent P−C bonds or P⋅⋅⋅C pnicogen bonds, but co-planar H(CH)P:C(OH) and HP:C(OH) are stabilized by O−H⋅⋅⋅P hydrogen bonds. The HXP:OHC complexes have non-coplanar structures that are also stabilized by P−C covalent bonds or pnicogen bonds. The H(CH)P:OHC and HP:OHC complexes in which the symmetry plane of the complex and the local symmetry plane of the carbene are perpendicular are stabilized by P⋅⋅⋅π bonds with P acting as the electron-pair donor to the OHC π system. The HXP:C(NH), HXP:C(OH), and HXP:OHC complexes are described in terms of their binding energies, charge-transfer energies, electron density properties, and equation-of-motion coupled cluster singles and doubles spin–spin coupling constants.
Versión del editorhttp://dx.doi.org/10.1002/cphc.201700187
URIhttp://hdl.handle.net/10261/168908
Identificadoresdoi: 10.1002/cphc.201700187
issn: 1439-4235
e-issn: 1439-7641
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