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The redox properties of (1,6-bis(benzimidazol-2-yl)-2,5-dithiahexane) chloro-copper(II) chloride as studied by cyclic voltammetry
Authors:M.F. Cabral  J.De O. Cabral  J.Van Rijn  J. Reedijk
Affiliation:Laboratorio Ferreira da Silva, Faculdade de Ciencias, 4000 Oporto, Portugal;Department of Chemistry, State University Leiden, P.O. Box 9502, 2300 RA Leiden, The Netherlands
Abstract:Cyclic voltammetry in acetonitrile has been used to study the redox properties of the compound [Cu-(BBDH)Cl] Cl under various conditions. The nature of the species in solution was studied with the aid of ligand-field spectra and ESR spectra. It appears that in CH3CN solution two Cu(II) species are predominating, viz. [Cu(BBDH)(CH3CN)x]2+ and Cu(BBDH)-Cl+. Minor species are dimeric in nature, such as [(BBDH)CuCl2Cu(BBDH)]2+, as easily seen from ESR. The relative amount of the two major species was varied using added LiCl, allowing us to determine the nature of both species. The redox potential of the species [Cu(BBDH)Cl]+ appeared to be 0.62 V (against a normal hydrogen electrode), which is very high for a Cu(II) compound and in the same area as found for the blue copper proteins. Re-oxidation of Cu(BBDH)+ in the presence of LiCl shows that Cl slowly recoordinates after reoxidation.
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