Coyle, Joanne L.; Elias, Horst; Herlinger, Erwin; Lange, Jürgen and Nelson, Jane
Electron self-exchange kinetics in two average-valence dicopper cryptates.
Journal of Biological Inorganic Chemistry, 6(3) pp. 285–291.
Electron self-exchange rates, reported for two average-valence dicopper cryptates are, at around 10(5) M-1 s(-1) at the high end of the range for small-molecule model compounds. The cross-exchange reaction rate, and those for oxidation with [Co(ox)(3)](3-) . are consistent with an outer-sphere reaction mechanism. Despite the necessity for copper-copper bond making and breaking in the course of redox for one of the cryptates, the self-exchange rate is not decreased relative to the other cryptate, showing that this step is not rate limiting.
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