D'Alessandro, Deanna M., and Keene, F. Richard (2004) A cautionary warning on the use of electrochemical measurements to calculate comproportionation constants for mixed-valence compounds. Dalton Transactions, 2004 (23). pp. 3950-3954.

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Abstract

The redox potentials for successive oxidations in a series of ligand-bridged dinuclear ruthenium complexes are shown to be dependent on the identity of the anion used as the electrolyte in the electrochemical measurements. Since the differences between these redox potentials (∆Eox) are often used to calculate the comproportionation equilibrium constants (Kc) in mixed-valence species—and therefore the extent of inter-metal communication between the metal centres—the results demonstrate the need for extreme care in comparison of ∆Eox data and of Kc values derived from them.

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