Electrochemical properties of [(C 5Me 5)Rh III(L)Cl] + complexes (L = 2,2′-bipyridine or 1,10-phenanthroline derivatives) in solution in related polypyrrolic films. Application to electrocatalytic hydrogen generation

• Published in: Journal of electroanalytical chemistry (Lausanne, Switzerland) Vol. 352; no. 1; pp. 213 - 228
• Main Authors: Chardon-Noblat, Sylvie, Cosnier, Serge, Deronzier, Alain, Vlachopoulos, Nicolas
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 15.06.1993; Elsevier Science
• Subjects: Applied sciences; Exact sciences and technology; Organic polymers; Physicochemistry of polymers; Properties and characterization; Special properties (catalyst, reagent or carrier); Electrocatalysis; Electrochemical properties; Rhodium Complexes; Hydrogen; Ligand; Preparation; Metallocene; Pyrrole polymer; Solution
• ISSN: 1572-6657; 1873-2569
• DOI: 10.1016/0022-0728(93)80265-J

Electrochemical characterization of a series of rhodium(III complexes [(C 5Me 5)Rh III(L)Cl] + containing a 2,2′-bipyridine or 1,10-phenanthroline derivative as the ligand L is described. The reduction involves a bielectronic reduction of the metal centre leading to [(C 5Me 5)Rh I(L)Cl] − which is in equilibrium with the chloro-less species [(C 5Me 5)Rh I(L)] 0. The relative amounts of the two compounds depend on the nature of the ligand L. Films of the corresponding substituted polypyrroles are prepared by oxidative polymerization of the complexes containing a pyrrole-ligand derivative. Immobilization of the complexes into a polymeric film allows the build up of the reactive species [(C 5Me 5)Rh III(L)] 2+ as a consequence of its slow coordination by the released chloro ligand into the polymeric form. The electrocatalytic ability of these polypyrrolic rhodium(III complex films for hydrogen evolution has been demonstrated.