Detailed understanding of the transition between localized and delocalized behaviour in mixed valence compounds has been elusive as evidenced by many interpretations of the Creutz–Taube ion, [(NH3)5Ru(pz)Ru(NH3)5]5+. In a review in 2001, experimental protocols and a systematic model to probe this region were proposed and applied to examples in the literature. The model included: (i) multiple orbital interactions in ligand-bridged transition metal complexes, (ii) inclusion of spin-orbit coupling which, for dπ5–dπ6complexes, leads to five low-energy bands, two from interconfigurational (dπ→dπ) transitions at the dπ5site and three from intervalence transfer transitions, (iii) differences in time scale between coupled vibrations and solvent modes which can result in solvent averaging with continued electronic asymmetry defining ‘class II–III’, an addition to the Robin–Day classification scheme, and (iv) delineation of coupled vibrations into barrier vibrations and ‘spectator’ vibrations. The latter provide direct insight into localization or delocalization and time scales for electron transfer. In this paper, the earlier model is applied to a series of mixed-valence molecules.