Glassy carbon modified by a silver-palladium alloy: cheap and convenient cathodes for the selective reductive homocoupling of alkyl iodides

Abstract

Micrometer-thick layers of silver-palladium alloy were elaborated in order to modify the surface of glassy carbon electrodes. Such a surface modification can be readily achieved via a preliminary silver galvanostatic deposit onto carbon followed by a 'palladization' step, thanks to a simple immersion in acidic PdII-based solutions producing a displacement reaction. The as-prepared metallic interfaces exhibit outstanding catalytic capabilities especially in the cleavage of carbon-halogen bonds while being chemically/electrochemically quite stable and relatively inexpensive. More specifically, the use of such glassy carbon/Ag-Pd electrodes in dimethylformamide (DMF) containing tetraalkylammonium salts (TAA+X-) makes the one-electron reductions of primary alkyl iodides possible; this reduction leads to the formation of homodimers in high yields. Formation of a free radical as transient resulted from the homocoupling reaction. © 2008 Elsevier Ltd. All rights reserved.