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Nonbonding pairs in cyclic thioethers: Electrostatic modeling and ab initio calculations for complexes of 2,5-dihydrothiophene, thietane, and thiirane with hydrogen fluoride

Research output: Contribution to journalArticle

Original languageEnglish
Article numbere25885
JournalInternational Journal of Quantum Chemistry
Volume119
Issue number10
Early online date20 Dec 2018
DOIs
DateAccepted/In press - 4 Dec 2018
DateE-pub ahead of print - 20 Dec 2018
DatePublished (current) - 15 May 2019

Abstract

Electrostatic potential energies V(ϕ) of a non-perturbing, protonic charge at fixed distances r from the S atom in three cyclic thioethers were examined as functions of the angles ϕ made by the r-vector with the C 2 axis (thiirane and 2,5-dihydrothiophene) or the local C 2 axis (thietane). The electrostatic PE V HF (ϕ) of HF (HF modelled as an extended electric dipole) was also calculated and the results compared with geometries of the thioether⋯HF complexes calculated at the CCSD(T)-F12c/cc-pVTZ-F12 level. The latter reveal angular deviations θ ∼10-20° of the S⋯HF nuclei from collinearity in directions suggesting secondary interactions of F with H atom(s) of the rings. Angles ϕ made by the S⋯H hydrogen bond with the C 2 (or local C 2 ) axes in the complexes are systematically larger (∼4-9°) than indicated by the V HF (ϕ) functions. Minima in the simple V(ϕ) versus ϕ functions occur at values smaller (∼5-10°) than those in the V HF (ϕ) curves.

    Research areas

  • cyclic thioethers, electrostatic potential energy

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    Rights statement: This is the accepted author manuscript (AAM). The final published version (version of record) is available online via Wiley at https://doi.org/10.1002/qua.25885 . Please refer to any applicable terms of use of the publisher.

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