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 Co(III) complex, [Co(III)LS(Cl)] (1; 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+) (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 M(n)2-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.
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). marcello.gennari@ujf-grenoble.fr.
Marcello
M
Gennari
Bertrand
B
Gerey
Nikita
N
Hall
Jacques
J
Pécaut
Marie-Noëlle
MN
Collomb
Mathieu
M
Rouzières
Rodolphe
R
Clérac
Maylis
M
Orio
Carole
C
Duboc
D003035:Cobalt / Q000737:chemistry*; D056831:Coordination Complexes / Q000737:chemistry; D018360:Crystallography, X-Ray; D055664:Electrochemical Techniques; D008280:Magnetics; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D013438:Sulfhydryl Compounds / Q000737:chemistry*
D056831:Coordination Complexes; D013438:Sulfhydryl Compounds; D003035:Cobalt; C027875:cobaltous sulfide
bioinorganic chemistry; cobalt complexes; disulfide/thiolate interconversion; sulfur ligands