Chalcogen–π interactions occur between a covalently bound chalcogen atom that enters into a non-covalent interaction with an unsaturated moiety, a bonding motif found in various structures, such as, proteins. In this work, we have systematically explored and analyzed chalcogen–π interactions in model systems X2D•••A (with D = O, S, Se, Te; X = halogen; A = acetylene, ethylene and 2-butyne), using relativistic density functional theory (DFT). The nature and trends in stability of the chalcogen–π bonds are analyzed and interpreted in terms of quantitative MO theory in combination with a matching canonical energy decomposition analysis (EDA) scheme. We find that chalcogen–π bonds increase in strength as the X–D electronegativity difference becomes greater. Moreover, 2-butyne was found to participate in the strongest non-covalent interaction due to enhanced orbital interactions.
Nature and strength of chalcogen-π bonds
Bortoli M.;Ahmad S. M.;Bickelhaupt F. M.;Orian L.
2018
Abstract
Chalcogen–π interactions occur between a covalently bound chalcogen atom that enters into a non-covalent interaction with an unsaturated moiety, a bonding motif found in various structures, such as, proteins. In this work, we have systematically explored and analyzed chalcogen–π interactions in model systems X2D•••A (with D = O, S, Se, Te; X = halogen; A = acetylene, ethylene and 2-butyne), using relativistic density functional theory (DFT). The nature and trends in stability of the chalcogen–π bonds are analyzed and interpreted in terms of quantitative MO theory in combination with a matching canonical energy decomposition analysis (EDA) scheme. We find that chalcogen–π bonds increase in strength as the X–D electronegativity difference becomes greater. Moreover, 2-butyne was found to participate in the strongest non-covalent interaction due to enhanced orbital interactions.
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