Evidence for a High-Valent Iron-Fluoride That Mediates Oxidative C(sp3)‐H Fluorination

(Fe(II)(NCCH₃)(NTB))(OTf)₂ (NTB = tris(2- benzimidazoylmethyl)amine, OTf = trifluoromethanesulfonate) was reacted with difluoro(phenyl)-λ³-iodane (PhIF₂) in the presence of a variety of saturated hydrocarbons, resulting in the oxidative fluorination of the hydrocarbons in moderate-to-good yields. Kinetic and product analysis point towards a hydrogen atom transfer oxidation prior to fluorine radical rebound to form the fluorinated product. The combined evidence supports the formation of a formally Fe(IV)(F)₂ oxidant that performs hydrogen atom transfer followed by the formation of a dimeric μ-F−(Fe(III))₂ product that is a plausible fluorine atom transfer rebound reagent. This approach mimics the heme paradigm for hydrocarbon hydroxylation, opening up avenues for oxidative hydrocarbon halogenation.