The redox properties of complexes of Pd(II), Cu(II) and Ni(II) with the N,N′-ethylenebis(acetylacetoniminate) ligand, [(acac)2en]2−, have been investigated by cyclic voltammetry, chronoamperometry and controlled potential coulometry in acetonitrile solvent at platinum and mercury electrodes. The one-electron oxidation product of [Pd{(acac)2en}] has been identified as the dimeric cation [Pd{(acac)2en}]22+; the cathodic reduction of the starting complex originates the corresponding Pd1 species, stable only in the voltammetric time-scale. The electrooxidation process of [Cu{(acac)2en}] leads to the short-lived corresponding [CuL]+ species, from which free Cu+ or Cu2+ ions generate, depending on the working potential; the overall cathodic process appears to be rather complicated. The [Ni{(acac)2en}] complex undergoes an irreversible one-electron oxidation in the voltammetric time-scale, while the overall anodic process gives rise to a doubly charged cationic species, from which the parent compound can be electrolytically regenerated. Comparisons with the previously reported voltammetric properties of N,N′-ethylenebis(monothioacetylacetoniminato) metal complexes have been done; the effect on EView the MathML source values of substitution of oxygen for sulphur in the atom donor set is outlined.
Voltammetric behaviour of transition metal complexes with extended - systems schiff base ligands / A., Cinquantini; Seeber, Renato; R., Cini; P., Zanello. - In: JOURNAL OF ELECTROANALYTICAL CHEMISTRY AND INTERFACIAL ELECTROCHEMISTRY. - ISSN 0022-0728. - STAMPA. - 134:(1982), pp. 65-73. [10.1016/S0022-0728(82)85027-4]
Voltammetric behaviour of transition metal complexes with extended - systems schiff base ligands
SEEBER, Renato;
1982
Abstract
The redox properties of complexes of Pd(II), Cu(II) and Ni(II) with the N,N′-ethylenebis(acetylacetoniminate) ligand, [(acac)2en]2−, have been investigated by cyclic voltammetry, chronoamperometry and controlled potential coulometry in acetonitrile solvent at platinum and mercury electrodes. The one-electron oxidation product of [Pd{(acac)2en}] has been identified as the dimeric cation [Pd{(acac)2en}]22+; the cathodic reduction of the starting complex originates the corresponding Pd1 species, stable only in the voltammetric time-scale. The electrooxidation process of [Cu{(acac)2en}] leads to the short-lived corresponding [CuL]+ species, from which free Cu+ or Cu2+ ions generate, depending on the working potential; the overall cathodic process appears to be rather complicated. The [Ni{(acac)2en}] complex undergoes an irreversible one-electron oxidation in the voltammetric time-scale, while the overall anodic process gives rise to a doubly charged cationic species, from which the parent compound can be electrolytically regenerated. Comparisons with the previously reported voltammetric properties of N,N′-ethylenebis(monothioacetylacetoniminato) metal complexes have been done; the effect on EView the MathML source values of substitution of oxygen for sulphur in the atom donor set is outlined.Pubblicazioni consigliate
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