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 H−F bond (in product) that drives HAT oxidation. prepared a dimeric FeIII(F)−F−FeIII(F) complex (1) by reacting [FeII(NCCH3)2(TPA)](ClO4)2 (TPA=tris(2-pyridylmethyl)amine) with difluoro(phenyl)-λ3-iodane (difluoroiodobenzene). 1 was sluggish oxidant, however, it readily activated reaction Lewis or Brønsted acids to yield monomeric [FeIII(TPA)(F)(X)]+ (2) where X=F/OTf. and 2 were characterized using NMR, EPR, UV/Vis, FT-IR spectroscopies mass spectrometry. remarkably reactive FeIII reagent for oxidative C−H activation, demonstrating rates hydrocarbon comparable most FeIV oxidants.