Reaction of copper(II) with ferrocene and 1,1 '-dimethylferrocene in aqueous acetonitrile: the copper(II/I) self-exchange rate
salts, redox reaction, kinetic parameters, ligands, solvents, copper, ferrocene, Dmfc, Marcus theory, trifluoromethanesulfonate salts
The kinetics of the reactions of copper(II) with ferrocene (Fc) and 1,1‘-dimethylferrocene (Dmfc) have been studied at 25 °C in aqueous acetonitrile (AN) containing 50−97.5 vol % AN. With increasing % AN, the rate constant increases along with the driving-force for the reaction. The results are analyzed in terms of Marcus theory to estimate the Cu(II/I) electron self-exchange rate constant (k11) for the system. Over the solvent range studied, the calculated k11 changes from 1.1 × 10-9 to 17 × 10-9 M-1 s-1, with an average value of 5 × 10-9. In addition, the structures of the trifluoromethanesulfonate salts of [Cu(AN)4]+, [Cu(OH2)2(AN)2]2+, and [Cu(AN)4]2+ are reported. It is found that the Cu−NCCH3 bond-length difference between the Cu(I) and Cu(II) oxidation states is only ∼0.02 Å.
Irangu, J.; Fergusson, M. J.; Jordan, R. B. “Reactions of Copper(II) with Ferrocene and 1,1΄Dimethylferrocene in Aqueous Acetonitrile: The Copper(II/I) Self‐ Exchange Rate”, Inorg. Chem. 2005, 44, 1619.
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