Hydroxylation of Aromatics with the Help of a Non-Haem FeOOH: A Mechanistic Study under Single-Turnover and Catalytic Conditions

Ferric–hydroperoxo complexes have been identified as intermediates in the catalytic cycle of biological oxidants, but their role as key oxidants is still a matter of debate. Among the numerous synthetic low‐spin FeIII(OOH) complexes characterized to date, [(L52)Fe(OOH)]2+ is the only one that has been isolated in the solid state at low temperature, which has provided a unique opportunity for inspecting its oxidizing properties under single‐turnover conditions. In this report we show that [(L52)Fe(OOH)]2+ decays in the presence of aromatic substrates, such as anisole and benzene in acetonitrile, with first‐order kinetics. In addition, the phenol products are formed from the aromatic substrates with similar first‐order rate constants. Combining the kinetic data obtained at different temperatures and under different single‐turnover experimental conditions with experiments performed under catalytic conditions by using the substrate [1,3,5‐D3]benzene, which showed normal kinetic isotope effects (KIE>1) and a notable hydride shift (NIH shift), has allowed us to clarify the role played by FeIII(OOH) in aromatic oxidation. Several lines of experimental evidence in support of the previously postulated mechanism for the formation of two caged FeIV(O) and OH. species from the FeIII(OOH) complex have been obtained for the first time. After homolytic OO cleavage, a caged pair of oxidants [FeIVO+HO.] is generated that act in unison to hydroxylate the aromatic ring: HO. attacks the ring to give a hydroxycyclohexadienyl radical, which is further oxidized by FeIVO to give a cationic intermediate that gives rise to a NIH shift upon ketonization before the final re‐aromatization step. Spin‐trapping experiments in the presence of 5,5‐dimethyl‐1‐pyrroline N‐oxide and GC‐MS analyses of the intermediate products further support the proposed mechanism. Oxidation by FeIII(OOH): Investigations on a genuine non‐haem FeIII(OOH) intermediate (see figure) in the presence of either aromatic substrates or the probe substrate [1,3,5‐D3]benzene has clarified the role played by FeIII(OOH) in aromatic oxidations. Evidence for the formation of two caged FeIV(O) and OH. species from FeIII(OOH) has been obtained for the first time. These oxidants act in unison to give phenol products with normal kinetic isotope effects and notable hydride shifts.