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2021
Journal Article
Titel
A bioinspired oxoiron(IV) motif supported on a N2S2 macrocyclic ligand
Abstract
A mononuclear oxoiron(IV) complex 1-trans bearing two equatorial sulfur ligations is synthesized and characterized as an active-site model of the elusive sulfur-ligated FeIV=O intermediates in non-heme iron oxygenases. The introduction of sulfur ligands weakens the Fe=O bond and enhances the oxidative reactivity of the FeIV=O unit with a diminished deuterium kinetic isotope effect, thereby providing a compelling rationale for nature's use of the cis-thiolate ligated oxoiron(IV) motif in key metabolic transformations.
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