We anticipate high-valent metal halide (X) species will be highly effective hydrogen atom transfer (HAT) oxidants because of the magnitude of the H–X bond (in the product) that drives HAT oxidation. We prepared dimeric FeIII(X)–X–FeIII(X) complexes by reacting [FeII(L)](ClO4)2 (L = ttripodal tetradentate polyamine) with difluoro(phenyl)-λ3-iodane (difluoroiodobenzene). FeIII(X)–X–FeIII(X) were sluggish oxidants, however, they were readily activated by reaction with Lewis or Brønsted acids to yield a monomeric [FeIII(L)(X)]+ complexes. The synthesised complexes were characterised using NMR, EPR, UV-vis, and FT-IR spectroscopies and mass spectrometry. [FeIII(L)(F)]+ was a remarkably reactive FeIII reagent for oxidative C–H activation, demonstrating reaction rates for hydrocarbon HAT comparable to the most reactive FeIII and FeIV oxidants. Criticially, we have identified methods for oxidative halogenation using comparable systems.

High-valent metal-halides as effective oxidising and halogenating reagents

Fall 2022 abstracts, posters, and presentations will launch in mid-September.

ACS Fall 2022

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.