A bioinspired oxoiron(IV) motif supported on a N2S2 macrocyclic ligand.
- Resource Type
- Article
- Authors
- Deutscher, Jennifer; Gerschel, Philipp; Warm, Katrin; Kuhlmann, Uwe; Mebs, Stefan; Haumann, Michael; Dau, Holger; Hildebrandt, Peter; Apfel, Ulf-Peter; Ray, Kallol
- Source
- Chemical Communications. 3/21/2021, Vol. 57 Issue 23, p2947-2950. 4p.
- Subject
- *KINETIC isotope effects
*DEUTERIUM
*OXYGENASES
- Language
- ISSN
- 1359-7345
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. [ABSTRACT FROM AUTHOR]