Abstract
The electrochemisty of the 2,2′-bipyridyl ruthenium complexes [Ru(Bipy) 3] n± has been examined in a series of solvents with varying dielectric constant. The potential separation between the +1/0 and 0/−1 redox steps increases with decreasing solvent polarity and decreasing ionic strength of the supporting electrolyte. Electrochemically generated [Ru(Bipy) 3] n (where n = 0 or −1) is kinetically labile in these low oxidation states and capable of reacting with the very high dielectric solvent N-methylacetamide via an E rC i mechanism; k f for the following chemical reaction is 0.31±0.15 s −1. Relationship is drawn between the dependence of the [Ru(Bipy) 3] potentials on solvent dielectric and the effect of local dielectric on protein redox potentials, and comment is made also on the solvent dependence of the potential of the ferricenium/ferrocene couple.
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