Summary
Copper(I) complexes [CuClL]2 (L=Py, 4-PhPy, 4-MePy, 4-Me2NPy, and 4-PhCOPy) react with dioxygen in dichloromethane according to the rate law: r=KD 1/2 k2 [CuClL]2 1/2[O2] where KD is the dissociation constant of the equilibrium [CuClL]2 ⇋2 CuCIL and k2 the second order rate constant of the reaction of the latter with dioxygen.
The KD values were determined by molecular weight measurements in dichloromethane and a correlation has been developed between the experimental rate constants obtained and the acid dissociation constants (pKa) for the ligands. The reaction fits a Hammett linear free energy relationship and the rate-determining step is attributed to the first electron transfer to the dioxygen molecule from the mononuclear copper(I) complex, which is influenced by changes in the electron density on the copper.
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Balogh-Hergovich, É., Speier, G. Reaction of copper(I) chloride pyridine complexes with dioxygen. A kinetic study. Transition Met Chem 7, 177–180 (1982). https://doi.org/10.1007/BF01035837
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DOI: https://doi.org/10.1007/BF01035837