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A bioinspired oxoiron(IV) motif supported on a N2S2 macrocyclic ligand
Jennifer Deutscher1, Philipp Gerschel2, Katrin Warm1
1Institut für Chemie Humboldt-Universität zu Berlin, Brook-Taylor-Str. 2, 12489, Berlin, Germany. kallol.ray@hu-berlin.de.
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[double bond, length as m-dash]O intermediates in non-heme iron oxygenases. The introduction of sulfur ligands weakens the Fe[double bond, length as m-dash]O bond and enhances the oxidative reactivity of the FeIV[double bond, length as m-dash]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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