Chemical oxidation of [Ru-2(6+)(3,6-DTBCat)(4)](2-) affords [n-Bu4N][Ru-2(3,6-DTBDiox)(4)]center dot acetone (2 center dot acetone). The oxidized species was characterized by X-ray crystallographic analysis and EPR, and the delocalization of the unpaired electron over the entire molecule was indicated. This example showed that the utilization of redox-active ligands into a Ru-2 complex expanded the degree of freedom in the electronic structure. DFT calculations support this view, and the spin population was estimated to be approximately 18% and 82% for the Ru-2 core and the four dioxolene ligands, respectively.