A Bio‐Inspired Switch Based on Cobalt(II) Disulfide/Cobalt(III) Thiolate Interconversion1. (9th April 2014)

• Record Type: Journal Article
• Authors: Gennari, Marcello; Gerey, Bertrand; Hall, Nikita; Pécaut, Jacques; Collomb, Marie‐Noëlle; Rouzières, Mathieu; Clérac, Rodolphe; Orio, Maylis; Duboc, Carole
• Is Part Of: Angewandte Chemie. Volume 126:Number 21(2014)
• Page Start: 5422
• Page End: 5425
• Publication Date: 2014-04-09
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201402125
• Languages: English
• ISSNs: 0044-8249

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Disulfide/thiolate interconversion supported by transition‐metal ions is proposed to be implicated in fundamental biological processes, such as the transport of metal ions or the regulation of the production of reactive oxygen species. We report herein a mononuclear dithiolate Co^III complex, [Co^IIILS(Cl)] (<bold>1</bold>; LS=sulfur containing ligand), that undergoes a clean, fast, quantitative and reversible Co^II disulfide/Co^III thiolate interconversion mediated by a chloride anion. The removal of Cl⁻ from the Co^III complex leads to the formation of a bis(μ‐thiolato) μ‐disulfido dicobalt(II) complex, [Co₂^{II, II}LSSL]²⁺ (<bold>2</bold>²⁺). The structures of both complexes have been resolved by single‐crystal X‐ray diffraction; their magnetic, spectroscopic, and redox properties investigated together with DFT calculations. This system is a unique example of metal‐based switchable M^{<italic>n</italic>}₂‐RSSR/2 M^{(<italic>n</italic>+1)}‐SR (M=metal ion, <italic>n</italic>=oxidation state) system that does not contain copper, acts under aerobic conditions, and involves systems with different nuclearities.</p> </abstract>