Issue 19, 2001
From the journal:

Journal of the Chemical Society, Dalton Transactions

Spectroelectrochemistry of potassium ethylxanthate, bis(ethylxanthato)nickel(ii) and tetraethylammonium tris(ethylxanthato)nickelate(ii)†

Ömer Dag,‡a   Seniz Özalp Yaman,§a   Ahmet M. Önal*a  and  Huseyin Isci*a  

* Corresponding authors

a Department of Chemistry, Middle East Technical University, 06531 Ankara, Turkey

Abstract

Electrochemical and chemical oxidation of S2COEt−, Ni(S2COEt)2, and [Ni(S2COEt)3]− have been studied by CV and in situ UV-VIS spectroscopy in acetonitrile. Cyclic voltammograms of S2COEt− and Ni(S2COEt)2 display one (0.00 V) and two (0.35 and 0.80 V) irreversible oxidation peaks, respectively, referenced to an Ag/Ag+ (0.10 M) electrode. However, the cyclic voltammogram of [Ni(S2COEt)3]− displays one reversible (−0.15 V) and two irreversible (0.35, 0.80 V) oxidation peaks, referenced to an Ag/Ag+ electrode. The low temperature EPR spectrum of the oxidatively electrolyzed solution of (NEt4)[Ni(S2COEt)3] indicates the presence of [NiIII(S2COEt)3], which disproportionates to Ni(S2COEt)2, and the dimer of the oxidized ethylxanthate ligand, (S2COEt)2 ((S2COEt)2  = C2H5OC(S)SS(S)COC2H5), with a second order rate law. The final products of constant potential electrolysis at the first oxidation peak potentials of S2COEt−, Ni(S2COEt)2, and [Ni(S2COEt)3]− are (S2COEt)2; Ni2+(sol) and (S2COEt)2; and Ni(S2COEt)2 and (S2COEt)2, respectively. The chemical oxidation of S2COEt− to (S2COEt)2, and [Ni(S2COEt)3]− to (S2COEt)2 and Ni(S2COEt)2 were also achieved with iodine. The oxidized ligand in the dimer form can be reduced to S2COEt− with CN− in solution.

Graphical abstract: Spectroelectrochemistry of potassium ethylxanthate, bis(ethylxanthato)nickel(ii) and tetraethylammonium tris(ethylxanthato)nickelate(ii)

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Article information

DOI
https://doi.org/10.1039/B105683M
Article type
Paper
Submitted
28 Jun 2001
Accepted
31 Jul 2001
First published
12 Sep 2001

J. Chem. Soc., Dalton Trans., 2001, 2819-2824

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Spectroelectrochemistry of potassium ethylxanthate, bis(ethylxanthato)nickel(II) and tetraethylammonium tris(ethylxanthato)nickelate(II)

Ö. Dag, S. Ö. Yaman, A. M. Önal and H. Isci, J. Chem. Soc., Dalton Trans., 2001, 2819 DOI: 10.1039/B105683M

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