Abstract
Ortho- as well as para-quinones were found to add oxidatively to the typical metal-centered radical, Co III(CN) 3− 5, producing in aprotic media radical adducts of Co(suIII) with p-semiquinone o monodentate o-semiquinone radical ligands, respectively. The electronic structure and bonding is quite similar in the adducts of both o- and p-quinones as is reflected by EPR and UV-VIS spectra. These radical adducts are rather labile, releasing free semiquinone radicals. The adduct of monodentate o-semiquinone represents a novel structural type of o-semiquinone bonding. It undergoes a slow follow-up intramolecular substitution reaction, producing a complex with the bidentate o-semiquinone radical ligand chelated to Co III.
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