Premium
Homonuclear chalcogen–chalcogen bond interactions in complexes pairing YO 3 and YHX molecules ( Y = S, Se; X = H, Cl, Br, CCH, NC, OH, OCH 3 ): Influence of substitution and cooperativity
Author(s) -
Esrafili Mehdi D.,
MohammadianSabet Fariba
Publication year - 2016
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.25076
Subject(s) - chemistry , chalcogen , atoms in molecules , molecule , ternary operation , crystallography , homonuclear molecule , natural bond orbital , stereochemistry , organic chemistry , computer science , programming language
MP2/aug‐cc‐pVTZ calculations are performed on complexes of YO 3 (Y = S, Se) with a series of electron‐donating chalcogen bases YHX (X = H, Cl, Br, CCH, NC, OH, OCH 3 ). These complexes are formed through the interaction of a positive electrostatic potential region (π‐hole) on the YO 3 molecule with the negative region in YHX. Interaction energies of the binary O 3 Y⋅⋅⋅YHX complexes are in the range of −4.37 to −12.09 kcal/mol. The quantum theory of atoms in molecules and the natural bond orbital analysis were applied to characterize the nature of interactions. It was found that the formation and stability of these binary complexes are ruled mainly by electrostatic effects, although the electron charge transfer from YHX to YO 3 unit also seems to play an important role. In addition, mutual influence between the Y⋅⋅⋅N and Y⋅⋅⋅Y interactions is studied in the ternary HCN⋅⋅⋅O 3 Y⋅⋅⋅YHX complexes. The results indicate that the formation of a Y⋅⋅⋅N interaction tends to weaken Y⋅⋅⋅Y bond in the ternary systems. Although the Y⋅⋅⋅Y interaction is weaker than the Y⋅⋅⋅N one, however, both types of interactions seem to compete with each other in the HCN⋅⋅⋅O 3 Y⋅⋅⋅YHX complexes. © 2016 Wiley Periodicals, Inc.