Abstract
The kinetics of oxidation of N,N′-ethylenebis(isonitrosoacetyleacetoneimine)copper(II) complex, CuIIL, by N-bromosuccinimide (SBr) in weakly aqueous acidic solutions was studied under pseudo-first-order conditions. Plots of ln(A ∞ − A t ) versus time where A t and A ∞ are absorbance values of the Cu(III) product at time t and infinity, respectively, showed marked deviations from linearity. The curves showed an acceleration of reaction rate consistent with an autocatalytic behavior. In the presence of Hg(II) ions, plots of ln(A ∞ − A t ) versus time are linear up to >85 % of reaction. The value of the observed rate constant, k obs, increases with decreasing pH. At constant reaction conditions, the dependence of the observed rate constants, k obs, is described by Eq. (1).
The dependence of both k o and k 1 on [SBr] is not linear. The mechanism of the title reaction is consistent with an inner sphere mechanism in which a pre-equilibrium step precedes the electron transfer step. The overall rate law is represented by Eq. (2) where [CuIIL]t and K 1 represent the total copper(II) complex concentration and the pre-equilibrium formation constant, respectively.
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Salih, I.M., Aljaber, A.S., Eltayeb, M.AZ. et al. Inner sphere oxidation of N,N′-ethylenebis(isonitrosoacetyleacetoneimine)copper(II) by N-bromosuccinimide in aqueous weakly acidic solutions. Transition Met Chem 38, 213–218 (2013). https://doi.org/10.1007/s11243-012-9680-6
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DOI: https://doi.org/10.1007/s11243-012-9680-6