Solvation effects on the structure and stability of alkali metal carbenoids

Dilchert, Katharina and Schmidt, Michelle and Großjohann, Angela and Feichtner, Kai-Stephan and Mulvey, Robert E. and Gessner, Viktoria H. (2021) Solvation effects on the structure and stability of alkali metal carbenoids. Angewandte Chemie International Edition, 60 (1). pp. 493-498. ISSN 1521-3773 (https://doi.org/10.1002/anie.202011278)

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Abstract

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 −10 °C in toluene. These divergent stabilities could be explained by the different structures formed in solution. In contrast to simple organolithium reagents, the monomeric THFsolvate 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 α-elimination.

ORCID iDs

Dilchert, Katharina, Schmidt, Michelle, Großjohann, Angela, Feichtner, Kai-Stephan, Mulvey, Robert E. ORCID logoORCID: https://orcid.org/0000-0002-1015-2564 and Gessner, Viktoria H.;
  • Item type:Article
    ID code:74082
    Dates:
    Date
    Event
    4 January 2021
    Published
    2 October 2020
    Published Online
    25 September 2020
    Accepted
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:05 Oct 2020 12:56
    Last modified:12 Nov 2024 01:13
    URI:https://strathprints.strath.ac.uk/id/eprint/74082
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