Rapid Iron(III)-Fluoride-Mediated Hydrogen Atom Transfer

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 characterized 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.