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Chalcogen Bonds In Complexes Of Soxy (X, Y = F, Cl) With Nitrogen Bases, Luis Miguel Azofra, Ibon Alkorta, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

SOF2, SOFCl, and SOCl2 were each paired with a series of N bases. The potential energy surface of the binary complexes were characterized by MP2 calculations with double and triple-ξ basis sets, extrapolated to complete sets. The most stable configurations contained a S···N chalcogen bond with interaction energies as high as 6.8 kcal/mol. These structures are stabilized by a Nlp→σ*(S−Z) electron transfer (Z = O, F, Cl), complemented by Coulombicattraction of N to theσ-hole opposite the Z atom. N···S−F and N···S−Cl chalcogen bonds are stronger than N···S = O interactions.Formation of each chalcogen bond elongates all of the internalcovalent bonds …