Stable Carbenes as Structural Components of Partially Saturated Sulfur-Containing Heterocycles |
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| Authors: | Alexander B Rozhenko Yuliia S Horbenko Andrii A Kyrylchuk Evgenij V Zarudnitskii Sergiy S Mykhaylychenko Yuriy G Shermolovich Andriy V Grafov |
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| Institution: | 1.Institute of Organic Chemistry, National Academy of Sciences, Murmanska Str. 5, 02094 Kyiv, Ukraine; (A.B.R.); (Y.S.H.); (A.A.K.); (E.V.Z.); (S.S.M.); (Y.G.S.);2.Igor Sikorsky Kyiv Polytechnic Institute, National Technical University of Ukraine, Prosp. Peremohy 37, 03056 Kyiv, Ukraine;3.Department of Chemistry, University of Helsinki, A.I.Virtasen Aukio 1, 00560 Helsinki, Finland |
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| Abstract: | Recently, an unusual elongation of the C-S bond was observed experimentally for some sulfur-containing heterocycles. Using a superior ab initio (SCS-MP2/cc-pVTZ) level of theory, we showed that the phenomenon can be explained by a contribution of a donor–acceptor adduct of a carbene with an unsaturated ligand. One may achieve further elongation of the C-S bond, eventually turning it to a coordinate one, by increasing the stability of each part of the system as, e.g., in the utmost case of spiro adducts with Arduengo carbenes. The effect of carbene stability was quantified by employing the isodesmic reactions of carbene exchange. |
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| Keywords: | stable carbenes ab initio calculations thiadiazolines bond elongation |
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