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 Fe(III)(OOH) complexes characterized to date, [(L(5)(2))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 [(L(5)(2))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-D(3)]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 Fe(III)(OOH) in aromatic oxidation. Several lines of experimental evidence in support of the previously postulated mechanism for the formation of two caged Fe(IV)(O) and OH(·) species from the Fe(III)(OOH) complex have been obtained for the first time. After homolytic O-O cleavage, a caged pair of oxidants [Fe(IV)O+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 Fe(IV)O 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.

The first example of a microcrystalline powder of a synthetic low-spin (LS) mononuclear Fe(III)(OOH) intermediate has been obtained by the precipitation of the [Fe(III)(L(5) (2))(OOH)](2+) complex at low temperature. The high purity of this thermally unstable powder is revealed by magnetic susceptibility measurements. EPR studies on this complex, in the solid state and also in frozen solution, are reported and reveal the coexistence of two related Fe(III)(OOH) species in both states. We also present a theoretical analysis of the g tensor for LS Fe(III) complexes, based on new perturbation equations. These simple equations provide distortion-energy parameters that are in good agreement with those obtained by a full-diagonalization calculation.