Spectroelectrochemical behaviour of the trinuclear [Ru3O(O2CCH3)6(isonicotinamide)3] cluster
- 1 October 1989
- journal article
- Published by Canadian Science Publishing in Canadian Journal of Chemistry
- Vol. 67 (10) , 1632-1635
- https://doi.org/10.1139/v89-250
Abstract
The [Ru3O(OOCCH3)6(isonicotinamide)3] cluster exhibits reversible electrochemical and spectroelectrochemical behaviour in acetonitrile solutions, associated with a series of successive μ-oxo RuIVRuIVRuIII/RuIVRu1IIRuIII/…/RuIIRuIIRuII redox couples with E0 = 2.16, 1.21, 0.19, −0.98, and −1.4 V versus SHE. The metal-isonicotinamide and metal–metal charge–transfer transitions shift to lower energies as the oxidation states of the ruthenium ions decrease. In alkaline aqueous solution, the μ-oxo RuIIIRuIIIRuII cluster can be reversibly reduced to the μ-oxo RuIIIRuIIRuII product (E0 = −0.85 V); however, below pH 4, the reduction proceeds according to two successive steps, yielding RIIIRIIRuII species with loss of the central oxygen ion. These species can be reoxidized in the reverse potential scan, regenerating the µ-oxo RuIIIRuIIIRuII complex. Keywords: ruthenium–acetate clusters, cluster spectroelectrochemistry, cluster electrochemistry, ruthenium–isonicotinamide complex, trinuclear cluster.Keywords
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