Primary haloalkanes can graft onto the surface of glassy carbon and reticulated vitreous carbon electrodes�originally considered to be chemically inert�via an SN2 mechanism. Grafting occurs in both cyclic voltammetry and controlled-potential electrolysis experiments with a variety of primary alkyl halides. Using 1,2,4,5-tetracyanobenzene as a mediator demonstrates that the cathodic peak potential shifts toward more negative values, whereas the anodic peak potential shifts toward more positive values, and both cathodic and anodic peak currents decrease as the density of the grafted species increases. Furthermore, the catalytic behavior of electrogenerated nickel(I) salen, used widely as a catalyst for the cleavage of carbon�halogen bonds, is significantly diminished on electrodes bearing grafted alkyl chains. This phenomenon has broad implications for controlled-potential electrolysis because the reduction potential of the substrate may change during electrolysis and because classic cleaning procedures for carbon surfaces are not sufficient to remove covalently grafted species.

Effect of alkyl groups electrolytically grafted onto vitreous carbon cathodes via reduction of haloalkanes on the catalytic behavior of nickel(I) and cobalt(I) salen

245th National Meeting (2013)

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