Synthesis and Spectroelectrochemical Characterization of a Novel Oxalate-Bridged Binuclear Ruthenium(III) Complex

A novel oxalate-bridged binuclear ruthenium(III) complex, [{Ru(acac)2}2(μ-ox)] (acac− = acetylacetonate and ox2− = oxalate), has been prepared via self-dimerization of K[Ru(acac)2(ox)] in aqueous solutions containing ferric salts as catalyst. The Ru2III,II mixed-valence species generated electrochemically with Kc=105.0 for the comproportionation constant exhibits a weak intervalence charge transfer (IVCT) band at 1430 nm. The IR spectra from spectroelectrochemistry indicate a partially localized mixed-valence state (Class II-III behavior).