Kinetic studies of the reduction of hexaaquacobalt(III) perchlorate by a cobaloxime, [Co(dmgBF2)2(H2O)2]

The reaction of View the MathML sourceCo(OH2)63+ with Co(dmgBF2)2(H2O)2 in 1.0 M HClO4/LiClO4 was found to be first-order in both reactants and the [H+] dependence of the second-order rate constant is given by k 2obs = b /[H+], b at 25 °C is 9.23 ± 0.14 × 102 s−1. The [H+] dependence at lower temperatures shows some saturation effect that allowed an estimate of the hydrolysis constant for View the MathML sourceCo(OH2)63+ as K a = 9.5 × 10−3 M at 10 and 15 °C. Marcus theory and the known self-exchange rate constant for Co(OH2)5OH2+/+ were used to estimate an electron self-exchange rate constant of k 22 = 1.7 × 10−4 M−1 s−1 for View the MathML source