Stable Carbenes as Structural Components of Partially Saturated Sulfur-Containing Heterocycles

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 unsatura...

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Autores principales: Rozhenko, Alexander B., Horbenko, Yuliia S., Kyrylchuk, Andrii A., Zarudnitskii, Evgenij V., Mykhaylychenko, Sergiy S., Shermolovich, Yuriy G., Grafov, Andriy V.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2022
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Article
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8911733/
https://www.ncbi.nlm.nih.gov/pubmed/35268558
http://dx.doi.org/10.3390/molecules27051458
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author Rozhenko, Alexander B.
Horbenko, Yuliia S.
Kyrylchuk, Andrii A.
Zarudnitskii, Evgenij V.
Mykhaylychenko, Sergiy S.
Shermolovich, Yuriy G.
Grafov, Andriy V.
author_facet Rozhenko, Alexander B.
Horbenko, Yuliia S.
Kyrylchuk, Andrii A.
Zarudnitskii, Evgenij V.
Mykhaylychenko, Sergiy S.
Shermolovich, Yuriy G.
Grafov, Andriy V.
author_sort Rozhenko, Alexander B.
collection PubMed
description 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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spelling pubmed-89117332022-03-11 Stable Carbenes as Structural Components of Partially Saturated Sulfur-Containing Heterocycles Rozhenko, Alexander B. Horbenko, Yuliia S. Kyrylchuk, Andrii A. Zarudnitskii, Evgenij V. Mykhaylychenko, Sergiy S. Shermolovich, Yuriy G. Grafov, Andriy V. Molecules Article 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. MDPI 2022-02-22 /pmc/articles/PMC8911733/ /pubmed/35268558 http://dx.doi.org/10.3390/molecules27051458 Text en © 2022 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Rozhenko, Alexander B.
Horbenko, Yuliia S.
Kyrylchuk, Andrii A.
Zarudnitskii, Evgenij V.
Mykhaylychenko, Sergiy S.
Shermolovich, Yuriy G.
Grafov, Andriy V.
Stable Carbenes as Structural Components of Partially Saturated Sulfur-Containing Heterocycles
title Stable Carbenes as Structural Components of Partially Saturated Sulfur-Containing Heterocycles
title_full Stable Carbenes as Structural Components of Partially Saturated Sulfur-Containing Heterocycles
title_fullStr Stable Carbenes as Structural Components of Partially Saturated Sulfur-Containing Heterocycles
title_full_unstemmed Stable Carbenes as Structural Components of Partially Saturated Sulfur-Containing Heterocycles
title_short Stable Carbenes as Structural Components of Partially Saturated Sulfur-Containing Heterocycles
title_sort stable carbenes as structural components of partially saturated sulfur-containing heterocycles
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8911733/
https://www.ncbi.nlm.nih.gov/pubmed/35268558
http://dx.doi.org/10.3390/molecules27051458
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