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Noncovalent Interactions in Complexes Involving the Cyclic C 2 H 2 X (X=O, S, Se) Molecules and the Lewis Acids YF (Y=F, Cl, Br, H)
Author(s) -
McDowell Sean A. C.,
Dong Wenbo,
Wang Yanqing,
Li Qingzhong
Publication year - 2019
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201901463
Subject(s) - natural bond orbital , electronegativity , chemistry , non covalent interactions , lewis acids and bases , crystallography , atoms in molecules , molecule , hydrogen bond , binding energy , density functional theory , interaction energy , stereochemistry , computational chemistry , physics , atomic physics , organic chemistry , catalysis , biochemistry
A computational study of the cyclic Lewis bases C 2 H 2 X (X=O, S, Se) interacting with the Lewis acids YF (Y=F, Cl, Br, H) in model C 2 H 2 X…YF dyads was undertaken. It was shown that the noncovalent X…Y interaction in these binary complexes increases with increasing YF dipole moment for the C 2 H 2 O complexes, but not for the C 2 H 2 S and C 2 H 2 Se complexes, where instead the X…Y interaction increases with increasing X/Y electronegativity difference. This suggests that electrostatic forces dominate the binding in the former, whereas polarization effects dominate in the latter complexes. These explanations were supported by natural bond orbital (NBO) and atoms in molecules (AIM) analyses of the electron density, as well as interaction energy decomposition analyses. A subsequent study of the cooperative effect of an additional hydrogen bond in the model triads, FH…C 2 H 2 X…YF and C 2 H 2 X…YF…HF, found that the X…Y interaction in the dyads is weakened in the former and strengthened in the latter, with the trends identified in the dyads persisting in both triads.