Abstract
The binuclear complexes (CN) 5 Fe(PyCN)Ru(NH 3 ) 5 − (III) were prepared by the substitution reactions of Ru(NH 3 ) 5 NCPy 2+ on Fe(CN) 5 OH 2 3− . Complexes III undergo nitrile hydrolysis to give mixed-valence species of the form (CH) 5 Fe(PyCONH)Ru(NH 3 ) 5 − (IV) when they are subjected to chemical oxidations of 1 equiv of peroxydisulfate. The results of UV-vis, IR, and electrochemical data suggest that complexes IV belong to a valence-trapped formulation containing the localized oxidation states Fe(II) and Ru(III). Rate constants of formation and dissociation of III and IV were measured, were consistent with kinetic results expected for the substitution of Fe(CN) 5 OH 2 3− with the divalent ligands
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