A detailed analysis of the reaction revealed that the reduction of Cu(dmp) 2 2+ involved the slow path related to the deformation of Cu(dmp) 2 2+ (path B in Scheme 1). The pseudo-first-order rate constant for the reduction reaction of Cu(dmp) 2 2+ by Fe(Cp) 2 was not linear against the concentration of excess amounts of Fe(Cp) 2. In contrast, we obtained the electron self-exchange rate constant of Cu(dmp) 2 2+/+ as 1.6 kg mol - 1 s - 1 from the reduction of Cu(dmp) 2 2+ by Co(bpy) 3 2+. It was shown that the electron self-exchange rate constants estimated for the Cu(dmp) 2 2+/+ couple from the oxidation reaction of Cu(dmp) 2 + by Ni(tacn) 2 3+ (5.9 × 10 2 kg mol - 1 s - 1) and Mn(bpyO 2) 3 3+ (2.9 × 10 4 kg mol - 1 s - 1) were consistent with the directly measured value by NMR (5 × 10 3 kg mol - 1 s - 1). Reduction reactions of Cu(dmp) 2 2+ (dmp = 2,9-dimethyl-1,10-phenanthroline) by ferrocene (Fe(Cp) 2 = bis(cyclopentadienyl)iron(II)), decamethylferrocene (Fe(PMCp) 2 = bis(pentamethylcyclopentadienyl)iron(II)), and Co(bpy) 3 2+ (bpy = 2,2 ‘-bipyridine) and oxidation reactions of Cu(dmp) 2 + by Ni(tacn) 2 3+ (tacn = 1,4,7-triazacyclononane) and Mn(bpyO 2) 3 3+ (bpyO 2 = N,N ‘-dioxo-2,2 ‘-bipyridine) were studied in acetonitrile for the purpose of interpreting the gated behavior involving copper(II) and -(I) species.
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