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Does single-electron chalcogen bond exist? Some theoretical insights

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Abstract

Ab initio calculations have been carried out to investigate the σ-hole interaction in XHY···CH3 and XHY···CH2CH3 complexes, where X = F, Cl, Br and Y = S, Se. This interaction, termed “single-electron chalcogen bond interaction” was analyzed in terms of geometric, interaction energies and electronic features of the complexes. This interaction is a weak one, with an interaction energy that varies from a minimum of -1.7 kcal mol-1 for BrHS···CH3 to -6.0 kcal mol-1 for FHSe···CH2CH3 at the CCSD(T)/aug-cc-pVTZ level of theory. Energy decomposition analysis indicated that the dominant attraction energy originates in the electrostatic term which is larger for the Se complexes than for the S counterparts. However, the attractive polarization and dispersion components also make an important contribution to the interaction energy for the single-electron chalcogen bond interactions.

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Authors and Affiliations

  1. Laboratory of Theoretical Chemistry, Department of Chemistry, University of Maragheh, 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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Fig. S1

Indicates the optimized structure of XHY···CH3 and XHY···CH2CH3 complexes (X=F, Cl, Br; Y=S, Se). (DOC 2220 kb)

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Esrafili, M.D., Mohammadian-Sabet, F. Does single-electron chalcogen bond exist? Some theoretical insights. J Mol Model 21, 65 (2015). https://doi.org/10.1007/s00894-015-2613-5

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  • DOI: https://doi.org/10.1007/s00894-015-2613-5

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