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Updated: Sep 30, 2025

Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
Published on: April 19, 2019
Stable Carbenes as Structural Components of Partially Saturated Sulfur-Containing Heterocycles
Alexander B Rozhenko1,2, Yuliia S Horbenko1,2, Andrii A Kyrylchuk1
1Institute of Organic Chemistry, National Academy of Sciences, Murmanska Str. 5, 02094 Kyiv, Ukraine.
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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