The ionic interactions were studied in aqueous solutions of Na(3)lrCl(6) + Pb(NO3)(2) in order to develop a facilitated electrosynthesis of iridium-based catalytic surfaces. Spectroscopic studies indicated that ion pair charge-transfer complexes [IrCl63-]-Pb(II) (K = 6 x 10(3)) and [Ir(H2O) Cl-5(2-)]-Pb(II) (K = 2 x 10(3)) were formed in fresh and aged solutions, respectively. Electrochemical studies showed that interactions between the Ir(H2O)Cl-5(2-) and Pb(II) species lead to synergistic lowering of the overpotential that was necessary for nucleation and growth of mixed metal oxide PbIrOx on the surface of glassy carbon electrodes. The Ir:Pb stoichiometry of the PbIrOx surface films was the same (1:1) as that of the high-temperature phase of Pb-Ir-O pyrochlore. Compared to IrOx, the PbIrOx films displayed enhanced catalytic activity toward the electrooxidation of carbohydrates. This was ascribed to synergism that involved retention of carbohydrate molecules at the Pb(II) sites of a PbIrOx film and oxidation at the adjacent Ir(IV) sites. The synergistic electroplating utilizing interactions between the partially aquated transition metal complex and posttransition metal ion represents a new synthetic route to highly homogeneous and reactive films of mixed metal oxides.