Grafting of ω-Alkyl Ferrocene Radicals to Carbon Surfaces By Means Of Electrocatalysis with Subnanomolar Transition-Metal (Pd, Pt, or Au) Layers

Authors

  • Prof. Viatcheslav Jouikov,

    Corresponding author
    1. Molecular Chemistry and Photonics, UMR 6226 Institut des Sciences Chimiques de Rennes, Université de Rennes 1, Campus de Beaulieu, 35042 Rennes (France), Fax: (+33) 2-323-6732
    • Molecular Chemistry and Photonics, UMR 6226 Institut des Sciences Chimiques de Rennes, Université de Rennes 1, Campus de Beaulieu, 35042 Rennes (France), Fax: (+33) 2-323-6732
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  • Prof. Jacques Simonet

    Corresponding author
    1. Equipe MaCSE, Institut des Sciences Chimiques de Rennes, CNRS, UMR 6226, Université de Rennes 1, Campus de Beaulieu, Bat. 10C, 35042 Rennes (France), Fax: (+33) 2-323-6755
    • Equipe MaCSE, Institut des Sciences Chimiques de Rennes, CNRS, UMR 6226, Université de Rennes 1, Campus de Beaulieu, Bat. 10C, 35042 Rennes (France), Fax: (+33) 2-323-6755
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Abstract

Electroreduction of ω-iodoalkyl ferrocenes (Fc-Cn-I) was achieved in non-aqueous media at carbon electrodes covered with extremely small amounts of transition metals (Γ≤10−9 mol cm−2) galvanostatically deposited onto the surface. Upon such a coverage with metals such as palladium, gold, platinum, and rhodium, the cleavage of the C[BOND]I bond becomes a one-electron process leading, within the potential range from −1.0 to −1.5 V vs. Ag/AgCl, to the formation of a free alkyl radical. The addition of these radicals onto the carbon surface may occur to a large extent at the graphitized zones (radical attack on Cmath image sites) and dense ferrocene layers, attached to the solid support by alkyl linkers, can thus be formed. Other metals such as copper, nickel, and cobalt were successfully used in this process. The residual metal deposits could be eliminated by simple sonication of the resulting carbon interfaces.

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