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

[FeII(NCCH3)(NTB)](OTf)2 (NTB = tris(2benzimidazoylmethyl)amine, OTf = trifluoromethanesulfonate) was reacted with difluoro(phenyl)-lambda 3-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 FeIV(F)2 oxidant that performs hydrogen atom transfer followed by the formation of a dimeric mu-F-(FeIII)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.