Structural and spectroscopic characterization of a diruthenium o-dioxolene complex possessing a singly occupied molecular orbital delocalized over the entire molecule, [Ru2(3,6-DTBDiox)4]-

Chemical oxidation of Ru2(6+)(3,6-DTBCat)4]2- affords n-Bu4N]Ru2(3,6-DTBDiox)4].acetone (2.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 Ru2 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 Ru2 core and the four dioxolene ligands, respectively.