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A Bio‐Inspired Switch Based on Cobalt(II) Disulfide/Cobalt(III) Thiolate Interconversion
Author(s) -
Gennari Marcello,
Gerey Bertrand,
Hall Nikita,
Pécaut Jacques,
Collomb MarieNoëlle,
Rouzières Mathieu,
Clérac Rodolphe,
Orio Maylis,
Duboc Carole
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201402125
Subject(s) - cobalt , chemistry , ligand (biochemistry) , metal , redox , ion , crystallography , oxidation state , metal ions in aqueous solution , sulfur , disulfide bond , copper , transition metal , oxygen , inorganic chemistry , crystal structure , catalysis , organic chemistry , biochemistry , receptor
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 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, [Co 2 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.