Journal of Electroanalytical Chemistry, Vol.420, No.1-2, 189-193, 1997
Configurational Stabilization of Mixed-Valence States in the Star-Burst Tetranuclear Ruthenium Complex Bridged with Acetylene Links
A new tetranuclear ruthenium complex in which a metal was bridged radially to three identical metals with acetylene links showed a mixed-valence state in cyclic voltammograms, The peak potential difference for the mixed-valence state was twice the potential difference for a mixed-valence state of the corresponding binuclear complex, This fact suggests stabilization of the mixed-valence state twice by configurational modification of redox centers. However, this is inconsistent with the prediction from the additive pair model of the redox interaction. A quantum chemical model of the redox interaction was presented, in which the potential difference was expressed by the overlap integral S and the nearest neighbor interaction energy between the reduced center and the oxidized one. Application of the theory gave a negative value of S, which demonstrated reasonably the stabilization of the mixed-valence state from a quantum chemical viewpoint.