Département de chimie moléculaire

The ruthenium $μ$-oxo bipyridyl dimer cis-[{\{}RuIII(bpy)2(OH2){\}}2O]4+ (1) (bpy=2,2'-bipyridine) is a remarkable catalyst for the oxidn. of water, chloride ion or org. compds. Only rare examples of immobilization of such catalysts on electrode surfaces have been reported; all attempts are based on the incorporation of 1 into thin polymeric films. These devices are reputed to have rather poor stability due to the leaching of the complex from the film. In this article, we report the syntheses of [{\{}RuIII(L)2(OH2){\}}2O]4+ complexes contg. substituted bpy ligands L (L=4-(4-pyrrol-1-yl-butyl)-4'-methyl-2,2'-bipyridine (L1), complex (2) or 4,4'-di-tert-butyl-2,2'-bipyridine (L2), complex (3)) from the corresponding mononuclear aquo precursors cis-[RuII(L1)2(H2O)2]2+ (4) and cis-[RuII(L2)2(H2O)2]2+ (5). Stable functionalized polypyrrole modified electrodes contg. the 2-core are obtained by anodic electropolymn. of solns. of 2 in the aprotic non-coordinating solvent CH2Cl2. Their electrochem. behavior in aq. media at several pH values is studied. Some examples of electroinduced transformations occurring within the polymeric films leading to the tailoring of modified electrodes of poly-4 and cis-[RuII(L1)2(CH3CN)2]2+ are also reported. [on SciFinder(R)]