9-Oxidophenalenone: A Noninnocent β-Diketonate Ligand?
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The redox systems [Ru(L)(bpy)2]k, [Ru(L)2(bpy)]m, and [Ru(L)3]n containing the potentially redox-active ligand 9-oxidophenalenone = L– were investigated by spectroelectrochemistry (UV–vis–near-IR and electron paramagnetic resonance) in conjunction with density functional theory (DFT) calculations. Compounds [Ru(L–)(bpy)2]ClO4 ([1]ClO4) and [Ru(L–)2(bpy)]ClO4 ([2]ClO4) were structurally characterized. In addition to establishing electron-transfer processes involving the RuII/RuIII/RuIV and bpy0/bpy•– couples, evidence for the noninnocent behavior of L– was obtained from [RuIV(L•)(L–)(bpy)]3+, which exhibits strong near-IR absorption due to ligand-to-ligand charge transfer. In contrast, the lability of the electrogenerated anion [Ru(L)2(bpy)]− is attributed to a resonance situation [RuII(L•2–)(L–)(bpy)]−/[RuII(L–)2 (bpy•–)]−, as suggested by DFT calculations.
