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

1996-06-26
Dag, O
Önal, Ahmet Muhtar
Isci, H
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.

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Citation Formats
O. Dag, A. M. Önal, and H. Isci, “Electrochemical and chemical oxidation of K(C2H5OCS2),[Ni(C2H5OCS2)(2)] and [N(C2H5)(4)][Ni(C2H5OCS2)(3)],” 1996, vol. 26, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/54397.