Equilibrating (L)Fe^III-OOAc and (L)Fe^V(O) Species in Hydrocarbon Oxidations by Bio-Inspired Nonheme Iron Catalysts Using H₂O₂ and AcOH.

ABSTRACT: Inspired by the remarkable chemistry of the family of Rieske oxygenase enzymes, nonheme iron complexes of tetradentate N4 ligands have been developed to catalyze hydrocarbon oxidation reactions using H₂O₂ in the presence of added carboxylic acids. The observation that the stereo- and enantioselectivity of the oxidation products can be modulated by the electronic and steric properties of the acid implicates an oxidizing species that incorporates the carboxylate moiety. Frozen solutions of these catalytic mixtures generally exhibit EPR signals arising from two S = 1/2 intermediates, a highly anisotropic g2.7 subset (g_max = 2.58 to 2.78 and Δg = 0.85-1.2) that we assign to an Fe^III-OOAc species and a less anisotropic g2.07 subset (g = 2.07, 2.01, an

SUBMITTER: Oloo WN 

PROVIDER: S-EPMC5768304 | biostudies-literature | 2017 Dec

REPOSITORIES: biostudies-literature