A Bio-Inspired Switch Based on Cobalt(II) Disulfide/Cobalt(III) Thiolate Interconversion

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, [CoIIIL...

Full description

Saved in:
Bibliographic Details
Published in:Angewandte Chemie International Edition 2014-05, Vol.53 (21), p.5318-5321
Main Authors: Gennari, Marcello, Gerey, Bertrand, Hall, Nikita, Pécaut, Jacques, Collomb, Marie-Noëlle, Rouzières, Mathieu, Clérac, Rodolphe, Orio, Maylis, Duboc, Carole
Format: Article
Language:English
Subjects:
Anions
bioinorganic chemistry
Biological
Chemical Sciences
Chlorides
Cleaning
Cobalt - chemistry
cobalt complexes
Coordination chemistry
Coordination Complexes - chemistry
Crystallography, X-Ray
Diffraction
disulfide/thiolate interconversion
Disulfides
Electrochemical Techniques
Magnetic properties
Magnetics
Mathematical analysis
Metal ions
Molecular Conformation
Oxidation-Reduction
Sulfhydryl Compounds - chemistry
sulfur ligands
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary: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+ (22+). 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. A switchable CoII2 disulfide/CoIII thiolate system (see scheme; filled circles show the color change) is stable under aerobic conditions. It offers the chance to understand the disulfide/thiolate interconversion supported by transition‐metal ions, which is proposed to be involved in various fundamental biological processes.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201402125