Hexa-coordinated copper(II)-thiolates-II. Synthesis and characterization of a copper(II) complex with a reversible oxidative response

Mandal, S. ; Shukla, R. ; Bharadwaj, P. K. (1992) Hexa-coordinated copper(II)-thiolates-II. Synthesis and characterization of a copper(II) complex with a reversible oxidative response Polyhedron, 11 (15). pp. 1855-1860. ISSN 0277-5387

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Official URL: http://www.sciencedirect.com/science/article/pii/S...

Related URL: http://dx.doi.org/10.1016/S0277-5387(00)83732-8

Abstract

Two air-stable copper(II) complexes of homoleptic hexadentate ligands with the N2S*2S2 (S* = thioether, S = thiolate) donor set have been isolated. These complexes are dark blue in colour owing to the presence of a strong absorption peak around 600 nm, attributable to the σ (thiolate) → copper(II) LMCT transition. In acetonitrile, one complex provides the first example for a copper(II)-thiolate complex of a reversible cyclic voltammogram with E ½ = 0.50 V (vs SCE). This reversible response is attributable to the oxidation of the complex. Controlled experiments to explore possible ligand oxidations indicate that the reversible response is possibly metal-centred. Exhaustive, controlled potential coulometry experiments at 0.7 V at room temperature give n = 1.02 e, signifying the cyclic response is a one-electron process. The other complex gives a quasi-reversible cyclic voltammogram with E ½ = 0.54 V (vs SCE).

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