Evidence for a High-Valent Iron-Fluoride That Mediates Oxidative C(sp(3))-H Fluorination

[Image: see text] [Fe(II)(NCCH(3))(NTB)](OTf)(2) (NTB = tris(2-benzimidazoylmethyl)amine, OTf = trifluoromethanesulfonate) was reacted with difluoro(phenyl)-λ(3)-iodane (PhIF(2)) 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.