1. Stable Carbenes as Structural Components of Partially Saturated Sulfur-Containing Heterocycles
- Author
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Alexander B. Rozhenko, Yuliia S. Horbenko, Andrii A. Kyrylchuk, Evgenij V. Zarudnitskii, Sergiy S. Mykhaylychenko, Yuriy G. Shermolovich, Andriy V. Grafov, Department of Chemistry, Doctoral Programme in Drug Research, Doctoral Programme in Chemistry and Molecular Sciences, and Doctoral Programme in Materials Research and Nanosciences
- Subjects
DERIVATIVES ,ab initio calculations ,Organic Chemistry ,116 Chemical sciences ,Pharmaceutical Science ,thiadiazolines ,Analytical Chemistry ,stable carbenes ,bond elongation ,Chemistry (miscellaneous) ,AUXILIARY BASIS-SETS ,Drug Discovery ,Molecular Medicine ,ACCURATE ,CCSD(T) ,Physical and Theoretical Chemistry ,RI-MP2 - 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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