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Solvation Effects on the Structure and Stability of Alkali Metal Carbenoids
Author(s) -
Dilchert Katharina,
Schmidt Michelle,
Großjohann Angela,
Feichtner KaiStephan,
Mulvey Robert E.,
Gessner Viktoria H.
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202011278
Subject(s) - carbenoid , chemistry , reactivity (psychology) , toluene , dimer , alkali metal , solvation , lithium (medication) , synthon , solvent , monomer , inorganic chemistry , reagent , computational chemistry , polymer chemistry , medicinal chemistry , organic chemistry , catalysis , pathology , rhodium , endocrinology , medicine , polymer , alternative medicine
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 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 α‐elimination.