Solvation effects on the structure and stability of alkali metal carbenoids

Katharina Dilchert, Michelle Schmidt, Angela Großjohann, Kai-Stephan Feichtner, Robert E. Mulvey, Viktoria H. Gessner

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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.
Original languageEnglish
Pages (from-to)493-498
Number of pages6
JournalAngewandte Chemie International Edition
Volume60
Issue number1
Early online date2 Oct 2020
DOIs
Publication statusPublished - 4 Jan 2021

Keywords

  • alkali metals
  • structure reactivity relationship
  • lithium
  • NMR spectroscopy
  • carbenoids

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