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Rapid Iron(III)-Fluoride Mediated Hydrogen Atom Transfer

Panda, C.; Doyle, L. M.; Gericke, R.; McDonald, A. R.

We anticipate high-valent metal fluoride species will be highly effective hydrogen atom transfer (HAT) oxidants because of the magnitude of the H–F bond (in the product) that drives HAT oxidation. We prepared a dimeric Fe(III)(F)–F–Fe(III)(F) complex (1) by reacting [Fe(II)(NCCH₃)₂(TPA)](ClO₄)₂ (TPA = tris-(2-pyridylmethyl)amine) with difluoro(phenyl)-λ3-iodane (difluoroiodobenzene). 1 was a sluggish oxidant, however, it was readily activated by reaction with Lewis or Brønsted acids to yield a monomeric [Fe(III)(TPA)(F)(X)] + complex (2) where X = F/OTf. 1 and 2 were characterised using NMR, EPR, UV-vis, and FT-IR spectroscopies and mass spectrometry. 2 was a remarkably reactive Fe III reagent for oxidative C–H activation, demonstrating reaction rates for hydrocarbon HAT comparable to the most reactive Fe III and Fe IV oxidants.

Keywords: high-valent oxidants; biomimetic; proton coupled electron transfer; fluoride oxidant

Publ.-Id: 33292