Reaction of copper(II) with ferrocene and 1,1 '-dimethylferrocene in aqueous acetonitrile: the copper(II/I) self-exchange rate

Irangu, Japhet; Ferguson, Michael J.; Jordan, Robert B.

Reaction of copper(II) with ferrocene and 1,1 '-dimethylferrocene in aqueous acetonitrile: the copper(II/I) self-exchange rate

Author

Irangu, Japhet

Ferguson, Michael J.

Jordan, Robert B.

Date

2005

Keywords

salts, redox reaction, kinetic parameters, ligands, solvents, copper, ferrocene, Dmfc, Marcus theory, trifluoromethanesulfonate salts

Abstract (summary)

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.

Publication Information

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.