DYNAMIC CONSEQUENCES OF IONIC PERMSELECTIVITY - RAPID EJECTION FROM NAFION COATINGS OF ANIONS GENERATED ELECTROCHEMICALLY FROM CATIONIC PRECURSORS

The binuclear, cationic complex (NH3)5CoIIIO2C-4-C5H4NRuIII(edta)+ (4-C5H4N = 4-pyridyl) was synthesized and incorporated as a counterion in Nafion coatings on glassy carbon electrodes. Reduction of the Co(III) center of the incorporated complex causes it to dissociate into mononuclear fragments, one of which is an anionic complex of RuII(edta). The loss of this complex from the polyanionic Nafion coating was monitored by cyclic voltammetry, and its rapid ejection was observed directly with the aid of a rotating ring-disk electrode. The stability and coordination chemistry of the binuclear complex are altered dramatically by its incorporation in Nafion. The origins of the unusual behavior observed are discussed. © 1990, American Chemical Society. All rights reserved.