Soluble Redox-Active Polymetallic Chains [Ru0(CO)(L)(bpy)m]n (bpy = 2,2′-bipyridine, L = PrCN, Cl−; m = 0, −1): Electrosynthesis and Characterization
Electrochemical and spectroelectrochemical techniques were employed to study in detail the formation and so far unreported spectroscopic properties of soluble electroactive molecular chains with nonbridged metal−metal backbones, namely, [{Ru0(CO)(PrCN)(bpy)}m]n (m = 0, −1) and [{Ru0(CO)(bpy)Cl}m]n (m = −1, −2; bpy = 2,2′-bipyridine). The precursors cis-(Cl)-[RuII(CO)(MeCN)(bpy)Cl2] (in PrCN) and mer-[RuII(CO)(bpy)Cl3]− (in tetrahydrofuran (THF) and PrCN) undergo one-electron reductions to reactive radicals [RuII(CO)(MeCN)(bpy•−)Cl2]− and [RuII(CO)(bpy•−)Cl3]2−, respectively. Both [bpy•−]-containing species readily electropolymerize on concomitant dissociation of two chloride ligands and consumption of a second electron. Along this path, mer-to-fac isomerization of the bpy-reduced trichlorido complex (supported by density functional theory calculations) and a concentration-dependent oligomerization process contribute to the complex reactivity pattern. In situ spectroelectrochemistry (IR, UV/vis) has revealed that the charged polymer [{Ru0(CO)(bpy)Cl}−]n is stable in THF, but in PrCN it converts readily to [Ru0(CO)(PrCN)(bpy)]n. An excess of chloride ions retards this substitution at low temperatures. Both polymetallic chains are completely soluble in the electrolyte solution and can be reduced reversibly to the corresponding [bpy•−]-containing species.
Références
- Titre
- Soluble Redox-Active Polymetallic Chains [Ru0(CO)(L)(bpy)m]n (bpy = 2,2′-bipyridine, L = PrCN, Cl−; m = 0, −1): Electrosynthesis and Characterization
- Type de publication
- Article de revue
- Année de publication
- 2009
- Auteurs
- Hartl, Frantisek, Renfrew Anna K., Lafolet Frédéric, Mahabiersing Taasje, Calhorda Maria Jose, Chardon Sylvie, Haukka Matti, and Deronizer Alain
- Revue
- Inorg. Chem.
- Volume
- 48
- Pagination
- 8233–8244
- ISSN
- 0020-1669
Soumis le 12 avril 2018