Binuclear 1,2,4,5-Tetraimino-3,6-diketocyclohexane Bis[bis(Bipyridine)ruthenium(II)] Redox Series

The reaction of the [Ru(bpy)2(MeOH)2]2+ cation (bpy = 2,2‘-bipyridine) with 1,2,4,5-tetraaminobenzene in the presence of trace water and oxygen yields the cation [(bpy)2Ru(1,2,4,5-tetraimino-3,5-diketocyclohexane)Ru(bpy)2]4+. This binuclear species undergoes ligand-based reductions, giving the 3+ and 2+ charged species. The X-ray structure, electrochemistry, ZINDO calculations, and NMR, ESR, UV/vis, and IR spectra were analyzed where possible, giving an electronic model of the binuclear species and some of its redox products. The X-ray structure reveals the [(bpy)2Ru] fragments symmetrically disposed across the 1,2,4,5-tetraimino-3,5-diketocyclohexane bridge in a molecule with Cs symmetry.