A dramatic push effect on the homolysis of FeIII(OOR) intermediates to form non-heme FeIV=O complexes.

TL;DR: Reactions of synthetic iron(IV)-oxo porphyrin pi-cation radicals and mononuclear non-heme Iron(IV-oxo complexes in oxygenation reactions have been discussed as chemical models of cytochrome P450 and non- heme iron enzymes to demonstrate how mechanistic developments in biomimetic research can help understanding of dioxygen activation and oxygen atom transfer reactions in nature.

TL;DR: In this paper, a review of the great successes in iron-oxo chemistry over the past decade is presented, detailing various efforts to obtain ironoxo complexes in high yield, and to delve into their diverse structural and spectroscopic properties.

TL;DR: A chronological perspective of the observations that contributed to the generation of the first non-heme iron(IV)-oxo complexes in high yield is provided and their salient properties to date are summarized.

TL;DR: This review discusses the main classes of known bleach catalysts and their possible modes of action and offers an alternative: Transition-metal catalysts offer an alternative.

TL;DR: High-resolution crystal structure reveals an iron-oxygen bond length of 1.646(3) angstroms, demonstrating that a terminal iron(IV)=oxo unit can exist in a nonporphyrin ligand environment and lending credence to proposed mechanisms of nonheme iron catalysis.

TL;DR: It is proposed that the FeIVO species derives from O—O bond heterolysis of an unobserved FeII(TPA)-acyl peroxide complex, and lends credence to the proposed participation of analogous species in the oxygen activation mechanisms of many mononuclear nonheme iron enzymes.

TL;DR: A spectroscopic methodology was developed that provides significant mechanistic insight into the reactivity of non-heme ferrous active sites and reveals a general mechanistic strategy used by these enzymes and differences in substrate and cofactor interactions dependent on their requirement for activation by iron.

TL;DR: In this paper, the authors demonstrate the hydroxylation of cycloalkanes at 25 °C by the syringe pump addition of tert-alkyl hydroperoxides (10 and 1 equiv based on catalyst) to deoxygenated acetonitrile containing cyclo-alkanes (0.64 M) and 0.61 mM of the catalyst, [FeIII2O(TPA)2(H2O)2]4+, is demonstrated to be a reaction which involves free alkyl radicals.