A Bio‐Inspired Switch Based on Cobalt(II) Disulfide/Cobalt(III) Thiolate Interconversion |
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Authors: | Dr. Marcello Gennari Bertrand Gerey Dr. Nikita Hall Dr. Jacques Pécaut Dr. Marie‐Noëlle Collomb Mathieu Rouzières Dr. Rodolphe Clérac Dr. Maylis Orio Dr. Carole Duboc |
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Affiliation: | 1. Université Joseph Fourier Grenoble 1/CNRS, Département de Chimie Moléculaire, UMR‐5250, Laboratoire de Chimie Inorganique Redox, Institut de Chimie Moléculaire de Grenoble FR‐CNRS‐2607, BP‐53, 38041 Grenoble Cedex 9 (France);2. Laboratoire de Reconnaissance Ionique et Chimie de Coordination, Service de Chimie Inorganique et Biologique (UMR E‐3 CEA/UJF,), CEA‐Grenoble, INAC, 17 rue des Martyrs 38054 Grenoble cedex 9 (France);3. CNRS, CRPP, UPR 8641, 33600 Pessac (France);4. Univ. Bordeaux, CRPP, UPR 8641, 33600 Pessac (France);5. Univ Lille Nord de France, UDSL, Laboratoire de Spectrochimie Infrarouge et Raman, CNRS UMR 8516, BP 83, Lille (France) |
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Abstract: | 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 CoIII complex, [CoIIILS(Cl)] ( 1 ; LS=sulfur containing ligand), that undergoes a clean, fast, quantitative and reversible CoII disulfide/CoIII thiolate interconversion mediated by a chloride anion. The removal of Cl? from the CoIII complex leads to the formation of a bis(μ‐thiolato) μ‐disulfido dicobalt(II) complex, [Co2II,IILSSL]2+ ( 2 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 Mn2‐RSSR/2 M(n+1)‐SR (M=metal ion, n=oxidation state) system that does not contain copper, acts under aerobic conditions, and involves systems with different nuclearities. |
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Keywords: | bioinorganic chemistry cobalt complexes disulfide/thiolate interconversion sulfur ligands |
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