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σ-Hole bond tunability in YO2X2:NH3 and YO2X2:H2O complexes (X = F, Cl, Br; Y = S, Se): trends and theoretical aspects

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Abstract

A σ-hole is defined as an electron-deficient region on the extension of a covalently bonded group IV–VII atoms. If the electronic density in the σ-hole is sufficiently low, then this region will have a positive electrostatic potential, which allows attractive noncovalent interactions with negative sites. SO2X2 and SeO2X2 (X = F, Cl and Br) have three Lewis acid sites of σ-hole located in the outermost of chalcogen atom and X end, participating in the chalcogen and halogen bonds with NH3 and H2O, respectively. MP2/aug-cc-pVTZ and M06-2X/aug-cc-pVTZ calculations reveal that for a given halogen atom, SeO2X2 forms stronger chalcogen bond interactions than SO2X2 counterpart. Almost a perfect linear relationship is evident between the interaction energies and the magnitudes of the product of most positive and negative electrostatic potentials. The interaction energies calculated by M06-2X and MP2 methods are almost consistent with each other.

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Authors and Affiliations

  1. Laboratory of Theoretical Chemistry, Department of Chemistry, University of Maragheh, P.O. Box 5513864596, Maragheh, Iran

    Mehdi D. Esrafili & Fariba Mohammadian-Sabet

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  1. Mehdi D. Esrafili
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  2. Fariba Mohammadian-Sabet
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Correspondence to Mehdi D. Esrafili.

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Esrafili, M.D., Mohammadian-Sabet, F. σ-Hole bond tunability in YO2X2:NH3 and YO2X2:H2O complexes (X = F, Cl, Br; Y = S, Se): trends and theoretical aspects. Struct Chem 27, 617–625 (2016). https://doi.org/10.1007/s11224-015-0594-8

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