Electrochemical and chemical oxidation of K(C2H5OCS2),[Ni(C2H5OCS2)(2)] and [N(C2H5)(4)][Ni(C2H5OCS2)(3)]


Dag O., Onal A. , Isci H.

NATO Advanced Study Institute on Cytotoxic, Mutagenic and Carcinogenic Potential of Heavy Metals Related to Human Environment, PRZESIEKA, Poland, 15 - 26 June 1996, vol.26, pp.579-590 identifier

  • Publication Type: Conference Paper / Full Text
  • Volume: 26
  • City: PRZESIEKA
  • Country: Poland
  • Page Numbers: pp.579-590

Abstract

Electrochemical and chemical oxidation of (Et-Xan(-)), [Ni(Et-Xan)(2)] and [Ni(Et-Xan)(3)](-) (Et-Xan(-) = C2H5OCS2- have been studied by Cyclic Voltammetry and in situ UV-Vis spectroscopy in acetonitrile at room temperature. Cyclic Voltammograms (CV) of Et-Xan(-) and Ni(Et-Xan)(2) display one (0.00 V) and two (0.35 and 0.80 V) irreversible oxidation peaks, respectively, referenced to Ag/Ag+(0.10 M) electrode. However, CV of Ni(Et-Xan)(3)(-) displays one reversible (-0.15 V) and two irreversible (0.35, 0.80 V) oxidation peaks, respectively, referenced to Ag/Ag+ electrode. The products of constant potential electrolysis at the first oxidation peak potentials of Et-Xan(-) and [Ni(Et-Xan)(2)] are the dimer of the oxidized ligand, (Et-Xan)(2) and Ni-(sol(2+)); and that of Ni(Et-Xan)(3)](-) are (Et-Xan)(2) and [Ni(Et-Xan)(2)]. Chemical oxidation of Et-Xan(-) and [Ni(Et-Xan)(3)](-) with iodine to (Et-Xan)(2) and (Et-Xan)(2)/[Ni(Et-Xan)(2)], were also achieved. The oxidized ligand in the dimer form can be reduced to Et-Xan(-) with CN- in solution. Our data do not support the formation of Ni(III) species at any oxidation stage.