Abstract
Many features of the structural, magnetochemical, spectral, electrochemical, and chemical behavior of transition metal complexes with redox-active dioxolene ligands indicate that most of them are valence-localized species with well defined and experimentally distinguishable metal- and dioxolene-oxidation states. The valence localization results mainly from large structural differences between individual oxidation states of the dioxolene ligands. It is shown that dioxolene complexes may be treated like weakly coupled mixed-valence compounds, and a qualitative “localized-valence” model is developed in order to interpret physical and chemical properties of dioxolene complexes, including their bistability, in a unifying way.

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