Summary
The oxidation of the cuprous complex, [Cu(bipy)2]ClO4, in nitromethane (NM) and acetonitrile (AN) solution was studied. The reaction rate was found to be first order in oxygen and second order in the copper(I) complex. When an excess of ligand was present with the cuprous complex, the observed rate constant, k0, was found to have a reciprocal dependence on the concentration of free bipyridine. The calculated first dissociation constants, KD, (7.6 · 10−4 and 1.4 · 10−5M for AN and NM) at 23 °C indicate that the cuprous complex is more dissociated in acetonitrile. However, the rate of oxidation is 50 times slower in this solvent. Using the K NMD value, the rate constants for the oxidation of the undissociated and dissociated species were found to be 21.5 and 2.1 · 103 M−2s−1, respectively.
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Zamudio, W., García, A.M. & Spodine, E. Oxidation of bis(bipyridine) copper(1+) by oxygen in a non-aqueous system. Part I. Nitromethane, acetonitrile. Transition Met Chem 8, 69–72 (1983). https://doi.org/10.1007/BF01036081
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DOI: https://doi.org/10.1007/BF01036081