Oxidations of 4‐ and 3‐Aminopyridinepentaammineruthenium(ii) Complexes by Ethylenediaminetetraacetatocobaltate(III)

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Redox reactions of Co(edta)− with Ru(NH3)5L2+ (L = 3‐ and 4‐aminopyridine (AmPy)) were found to follow an outer‐sphere electron transfer mechanism. The specific rate constants are (3.26 ± 0.03) × 102 and (3.07 ± 0.04) × 103 M−1S−1, for L = 3‐ and 4‐AmPy, respectively, at μ, = 0.10 M LiClO4, pH = 8.0 (tris) and T = 25 °C. The rate constants of oxidations for a series of Ru(NH3)5L2+ complexes are higher than those of the corresponding Fe(CN)5L3‐ complexes by factors of 4 to 15 even after corrections for differences in reduction potentials and in charges of the complexes. Nonadiabaticity in the reactions of Fe(CN)5L3 complexes may account for the difference in the relative reactivities.