Bis(dioxolene)(bipyridine)ruthenium Redox Series

Article abstract of DOI:10.1021/ja00232a020

Complexes of the general formula ⁿ⁺ have been prepared where (bpy) is 2,2'-bipyridine and n = -1, 0, +1.The dioxolene ligand is 1,2-dihydroxybenzene (cathechol), 3,5-di-tert-butyl- or 3,4,5,6-tetrachloro-1,2-dihydroxybenzene which may formally exist in the catecholate, semiquinone, or quinone oxidation state.Redox series of up to five members have been prepared by controlled potential electrolysis of the parent species or, in some cases, by chemical oxidation or reduction.Electrochemistry, magnetism, X-ray structural data and ultraviolet, visible and near infrared electronic, resonance Raman, vibrational (FTIR), nuclear magnetic resonance, electron spin resonance and photoelectron spectra, for various members of the redox series, are discussed in terms of theelectronic structures (effective oxidation states, delocalization) of the complexes.Apparent conflicts between results obtained with different techniques are resolved by using a simple, quantitative MO model.