An Interpretation of Gated Behavior: Kinetic Studies of the Oxidation and Reduction Reactions of Bis(2,9-dimethyl-1,10-phenanthroline)copper(I/II) in Acetonitrile.

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. 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 x 10(2) kg mol(-)(1) s(-)(1)) and Mn(bpyO(2))(3)(3+) (2.9 x 10(4) kg mol(-)(1) s(-)(1)) were consistent with the directly measured value by NMR (5 x 10(3) kg mol(-)(1) s(-)(1)). 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+). 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). 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). By using Fe(PMCp)(2) (the E degrees value is 500 mV more negative than that of Fe(Cp)(2)(+/0)) as the reductant, the mixing with another pathway involving deformation of Cu(dmp)(2)(+) (path A in Scheme 1) became more evident. The origin of the "Gated Behavior" is discussed by means of the energy differences between the "normal" and deformed Cu(II) and Cu(I) species: the difference in the crystal field activation energies corresponding to the formation of pseudo-tetrahedral Cu(II) from tetragonally distorted Cu(II) and the difference in the stabilization energies of the tetrahedral and tetragonal Cu(I) for the activation of Cu(I) species. The reduction reaction of Cu(dmp)(2)(2+) by Fe(PMCp)(2) confirmed that the mixing of the two pathways takes place by lowering the energy level corresponding to the less favorable conformational change of Cu(I) species.