Triple halide-bridged diruthenium complexes in higher oxidation states

Abstract

The NBuⁿ₄⁺ salt of [Ru₂^III,IIIBr₉]^3– is soluble in organic solvents and electrochemical studies in CH₂Cl₂–0.50 mol dm^–3[NBuⁿ₄][BF₄] at 233 K show it to have three reversible, one-electron processes: namely oxidations at +0.83 and +1.36 V and a reduction at –0.60 V. Preparative-scale electrogeneration of the [Ru₂^III,IVBr₉]^2– and [Ru₂^IV,IVBr₉]^– ions has been achieved, and variable-temperature magnetic measurements on anolyte solutions of the former (µ_eff.= 4.40 µ_B per molecule at 273 K) indicate three unpaired electrons per molecule.