The unsymmetrical dinuclear rutheniumiron complexes [(NH3)5RubtaFe(CN)5]n (where bta = benzotriazolate; n = 2, 1, 0) were prepared as solid sodium salts from [RuII(NH3)5(bta)]+ or [RuIII(NH3)5(bta)]2+ and [FeII(CN)5(H2O)]3 and characterized in aqueous solution by means of electrochemical and spectroelectrochemical methods. UV-vis, near-infrared, IR, and cyclic and differential pulse voltammetry data suggest that the related mixed valent species belong to a valence trapped formulation, featuring localized Ru(III) and Fe(II) oxidation states. In spite of the class II categorization in the Robin and Day scheme, this system shows a remarkable metalmetal electronic coupling, as deduced from an intense, low-energy, and very broad intervalence band in the near-IR region. In addition, the mixed valence state displays enhanced stabilization in relation to the isovalent state. The intervalence transfer properties are discussed on the basis of Hush's theory.Key words: ammineruthenium complexes, cyanoiron complexes, mixed valence, intervalence, benzotriazole, benzotriazolate.
