Solvation effects on the structure and stability of alkali metal carbenoids

  • s-Block metal carbenoids are carbene synthons and applied in a myriad of organic transformations. They exhibit a strong structure–activity relationship, but this is only poorly understood due to the challenging high reactivity and sensitivity of these reagents. Here, we report on systematic VT and DOSY NMR studies, XRD analyses as well as DFT calculations on a sulfoximinoyl-substituted model system to explain the pronounced solvent dependency of the carbenoid stability. While the sodium and potassium chloride carbenoids showed high stabilities independent of the solvent, the lithium carbenoid was stable at room temperature in THF but decomposed at 108C in toluene. These divergent stabilities could be explained by the different structures formed in solution. In contrast to simple organolithium reagents, the monomeric THF-solvate was found to be more stable than the dimer in toluene, since the latter more readily forms direct Li/Cl interactions which facilitate decomposition via a-elimination.

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Author:Katharina DilchertGND, Michelle SchmidtGND, Angela GroßjohannGND, Kai-Stephan FeichtnerGND, Robert E. MulveyORCiDGND, Viktoria Däschlein-GessnerORCiDGND
Parent Title (German):Angewandte Chemie International Edition
Place of publication:Weinheim
Document Type:Article
Date of Publication (online):2024/02/21
Date of first Publication:2020/12/22
Publishing Institution:Ruhr-Universität Bochum, Universitätsbibliothek
Tag:NMR spectroscopy; alkali metals; carbenoids; lithium; structure-reactivity relationship
First Page:493
Last Page:498
Dieser Beitrag ist auf Grund des DEAL-Wiley-Vertrages frei zugänglich.
Institutes/Facilities:Lehrstuhl für Anorganische Chemie II
Dewey Decimal Classification:Naturwissenschaften und Mathematik / Chemie, Kristallographie, Mineralogie
open_access (DINI-Set):open_access
faculties:Fakultät für Chemie und Biochemie
Licence (English):License LogoCreative Commons - CC BY 4.0 - Attribution 4.0 International