Titre :

Theoretical investigation on the improper hydrogen bond in κ-carrabiose⋯Y (Y\u2009=\u2009HF, HCl, HBr, NH<sub>3<\/sub>, H<sub>2<\/sub>O, and H<sub>2<\/sub>S) complexes

Auteur(s) :

Fodil, Rachida [Auteur]
SAYEDE, Adlane [Auteur]
Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181
Sekkal-Rahal, Majda [Auteur]

Titre de la revue :

Journal of Molecular Modeling

Nom court de la revue :

J Mol Model (Online)

Numéro :

27

Éditeur :

Springer Verlag (Germany)

Date de publication :

2021-09-21

ISSN :

1610-2940

Discipline(s) HAL :

Chimie

Résumé en anglais : [en]

The nature of H-bonds in κ-carrabiose⋯Y (Y\u2009=\u2009HF, HCl, HBr, NH<sub>3<\/sub>, H<sub>2<\/sub>O, and H<sub>2<\/sub>S) complexes was studied. For this aim, the structure of isolated κ-carrabiose was optimized using ...
Lire la suite >The nature of H-bonds in κ-carrabiose⋯Y (Y\u2009=\u2009HF, HCl, HBr, NH<sub>3<\/sub>, H<sub>2<\/sub>O, and H<sub>2<\/sub>S) complexes was studied. For this aim, the structure of isolated κ-carrabiose was optimized using three global hybrids functional: B<sub>3<\/sub>LYP, PBE0, and M06-2X combined with 6-311G** basis set. Subsequently, the κ-carrabiose in the presence of HF, HCl, HBr, NH<sub>3<\/sub>, H<sub>2<\/sub>O, and H<sub>2<\/sub>S was optimized using the CBS-4 M method. NBO analyses were then carried out at the MP2\/6-311G** level of theory. A particular interest was focused on C<sub>(18)<\/sub>\u2015H<sub>(34)<\/sub>⋯Y bond. The results reveal that the C<sub>(18)<\/sub>\u2015H<sub>(34)<\/sub>⋯Y bond is an improper H-bond since a significant contraction of C<sub>(18)<\/sub>\u2015H<sub>(34)<\/sub> was observed during the complexation leading to a significant blueshifted stretching frequency. The NBO analyses have shown that the formation of the improper H-bonds C<sub>(18)<\/sub>\u2015H<sub>(34)<\/sub>⋯Y (Y\u2009=\u2009F, Cl, Br, N, O, and S) is principally due to the increase of the s-character of the hybrid orbital in carbon atom (rehybridization) in κ-carrabiose⋯Y complexes. Regarding the polarization, it was proved that more the H-bond center (carbon in C<sub>(18)<\/sub>\u2015H<sub>(34)<\/sub>⋯Y) becomes less positive, the hydrogen more positive, and Y more negative; more the contraction of the C<sub>(18)<\/sub>\u2015H<sub>(34)<\/sub> bond is important. It was also confirmed for intramolecular H-bonds in κ-carrabiose⋯Y complexes that the rehybridization is responsible for H-bonds nature either proper or improper.Lire moins >

Langue :

Anglais

Audience :

Internationale

Vulgarisation :

Non

Établissement(s) :

CNRS
Centrale Lille
ENSCL
Univ. Artois
Université de Lille

Collections :

• Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181

Équipe(s) de recherche :

Couches minces & nanomatériaux (CMNM)

Date de dépôt :

2022-03-08T13:51:06Z