Département de chimie moléculaire

The electrochem. behavior of [RuII(L)(CO)2Cl2], [RuII(L)(CO)Cl3][Me4N] and [RuII(L)(CO)2(MeCN)2][CF3SO3]2 (L = 2,2'-bipyridine or 4,4'-isopropoxycarbonyl-2,2'-bipyridine) was studied in MeCN. The oxidn. of [Ru(L)(CO)2Cl2] produces [RuIII(L)(CO)(MeCN)2Cl]2+ as a consequence of the instability of the electrogenerated transient RuIII species [RuIII(L)(CO)2Cl2]+. But the oxidn. of [RuII(L)(CO)Cl3][Me4N] produces the stable [RuIII(L)(CO)Cl3]. In contrast [RuII(L)(CO)2(MeCN)2][CF3SO3]2 is not oxidized in the range up to the most pos. potentials achievable. The redn. of [RuII(L)(CO)2Cl2] and [RuII(L)(CO)2(MeCN)2][CF3SO3]2 gave identical dark blue strongly adherent electroactive films. These films exhibit the characteristics of a metal-metal bond dimer structure. No films are obtained on redn. of [RuII(L)(CO)Cl3][Me4N]. The effect of the substitution of the bipyridine ligand by electron-withdrawing carboxy ester groups on the electrochem. behavior of all these complexes also was studied. [on SciFinder(R)]