A bioinspired oxoiron(IV) motif supported on a N2S2 macrocyclic ligand

Jennifer Deutscher; Philipp Gerschel; Katrin Warm; Uwe Kuhlmann; Stefan Mebs; Michael Haumann; Holger Dau; Peter Hildebrandt; Ulf-Peter Apfel; Kallol Ray

doi:10.1039/D1CC00250C

A bioinspired oxoiron(iv) motif supported on a N₂S₂ macrocyclic ligand†

Jennifer Deutscher,

^a Philipp Gerschel,^b Katrin Warm,

^a Uwe Kuhlmann,^c Stefan Mebs,

^d Michael Haumann,

^d Holger Dau,

^d Peter Hildebrandt,

^c Ulf-Peter Apfel

*^be and Kallol Ray

*^a

Author affiliations

* Corresponding authors

^a Institut für Chemie Humboldt-Universität zu Berlin, Brook-Taylor-Str. 2, Berlin, Germany
E-mail: kallol.ray@hu-berlin.de

^b Anorganische Chemie 1 Ruhr-Universität Bochum, Universitätsstraße 150, Bochum, Germany

^c Institut für Chemie Technische, Universität Berlin, Fakultät II Straße des 17, Juni 135, Berlin, Germany

^d Institut für Physik Freie, Universität Berlin, Arnimallee 14, 14195 Berlin, Germany

^e Department of Electrosynthesis, Fraunhofer UMSICHT, Osterfelder Str. 3, 46047 Oberhausen, Germany

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 Fe^IV [double bond, length as m-dash] O intermediates in non-heme iron oxygenases. The introduction of sulfur ligands weakens the FeO bond and enhances the oxidative reactivity of the Fe^IVO 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.

This article is part of the themed collection: Bioinspired metal complexes for chemical transformations and catalysis

Chemical Communications

A bioinspired oxoiron(iv) motif supported on a N₂S₂ macrocyclic ligand†

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A bioinspired oxoiron(IV) motif supported on a N₂S₂ macrocyclic ligand

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