Abstract
A subset of the large family of nonheme iron oxygenases carries out the oxidative decarboxylation of α-ketocarboxylate and α-hydroxycarboxylate substrates in the presence of O2. Iron complexes of α-ketocarboxylates and α-hydroxycarboxylates supported by tridentate and tetradentate ligands have been synthesized to act as functional models for these enzymes, and several have been structurally characterized. From studies of these model complexes and their reactivity toward various probe substrates, insights into the reaction mechanisms have been obtained, where iron(III)-superoxo and iron(IV)-oxo species have been implicated as key oxidants.
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