Cobalt Fluorocarbene Complexes

Unusual nucleophilic cobalt fluorocarbene complexes ([CoI]CFR; R = F, CF3) are described. Only a handful of fluorocarbenes of first-row transition metals have been reported, and these have exhibited electrophilic reactivity at the metal–carbene bonds. The title compounds are the first persistent/isolable cobalt fluorocarbenes and also rare examples of metal fluorocarbenes with relatively nucleophilic MC bonds (vs other metal fluorocarbene complexes), demonstrated by their reactions with H+ and Me+ and their unusual stability toward water. X-ray crystal structures reveal the shortest terminal cobalt–carbene bonds reported to date, and DFT studies provide details into the nature of these bonds.