Taming Metal/Fluorine Carbenoids

Abstract

Although Li/Cl carbenoids are versatile reagents in organic synthesis, the controlled handling of the extremely reactive and labile M/F carbenoids remains a challenge. We now show that even these compounds can be stabilized and isolated in solid state, as well as in solution. Particularly the sodium and potassium compounds exhibit a remarkable stability, thus allowing the first isolation of a room-temperature-stable fluorine carbenoid. Spectroscopic, as well as DFT studies confirmed the pronounced carbenoid character, showing M-F-C interactions with elongated C-F bonds. The different stabilities of the carbenoids was found to originate from the different strength of the M-F interaction. Hence, the lithium compounds are considerably more reactive than their heavier congeners. Reactivity studies showed that the nature of the metal also influences the reactivity, resulting in different selectivity in the addition to thioketones.

Keywords: alkali metals; carbanions; carbenoids; fluorine; structure-reactivity relationships.