"Resolving the Two-Electron Process for the Couple [(C5Me5)M(N^N)Cl]+/[(C5Me5)M(N^N)], (M = Rh , Ir) into Two One-Electron Steps Using the 2,2''''-Azobis(pyridine) N^N Ligand, Fast Scan Cyclovoltammetry and Spectroelectrochemistry: Detection of Radicals I"@en . "[EE99408C9ABE]" . "US - Spojen\u00E9 st\u00E1ty americk\u00E9" . "1"^^ . "Resolving the Two-Electron Process for the Couple [(C5Me5)M(N^N)Cl]+/[(C5Me5)M(N^N)], (M = Rh , Ir) into Two One-Electron Steps Using the 2,2''''-Azobis(pyridine) N^N Ligand, Fast Scan Cyclovoltammetry and Spectroelectrochemistry: Detection of Radicals I" . . "Kaim, W." . . . . "625426" . . "Resolving the Two-Electron Process for the Couple [(C5Me5)M(N^N)Cl]+/[(C5Me5)M(N^N)], (M = Rh , Ir) into Two One-Electron Steps Using the 2,2''''-Azobis(pyridine) N^N Ligand, Fast Scan Cyclovoltammetry and Spectroelectrochemistry: Detection of Radicals I"@en . . "N/A" . . . . . "Resolving the Two-Electron Process for the Couple [(C5Me5)M(N^N)Cl]+/[(C5Me5)M(N^N)], (M = Rh , Ir) into Two One-Electron Steps Using the 2,2''''-Azobis(pyridine) N^N Ligand, Fast Scan Cyclovoltammetry and Spectroelectrochemistry: Detection of Radicals I" . . "RIV/61388955:_____/03:54030108!RIV/2004/AV0/A54004/N" . "P(GA203/03/0821), Z(AV0Z4040901)" . "2240;2244" . . "0276-7333" . "RIV/61388955:_____/03:54030108" . "Organometallics" . "Fiedler, Jan" . . . "22" . . "The complex cations [(C5Me5)M(abpy)Cl]+, M = Rh or Ir, abpy = 2,2''''''''azobispyridine, are reduced to the coordinatively unsaturated compounds [(C5Me5)M(abpy)] via EPR- and UV/VIS-spectroelectrochemically detectable radical intermediates [(C5Me5)MIII(abpy-I)Cl];. Fast-scan cyclic voltammetry allowed us to establish the electrochemical potentials. This stepwise mechanism differs from the two-electron processes observed for analogous systems [(C5Me5)M(N^N)Cl]+/[(C5Me5)M(N^N)] with N^N = 2,2bipyridines, bidiazines or 1,4-diaza-1,3-butadienes. In contrast to cobalt systems like [(C5Me5)Co(bpy)Cl]+ the one-electron reduction does not involve the metal. The role of the abpy ligand as intermediate one-electron storage component for a metal-centered two-electron process is discussed. Further reduction of [(C5Me5)M(abpy)] to [(C5Me5)MII(abpy-II)]- at very negative potentials illustrates the extremely strong ; back donation from the 14 valence electron fragments (C5Me5)M, M = Rh or Ir."@en . . "Greulich, S." . "Reinhardt, R." . "4"^^ . "0"^^ . "electrochemical generation; iridium(III) complexes; bridging ligands"@en . "5"^^ . . "0"^^ . "The complex cations [(C5Me5)M(abpy)Cl]+, M = Rh or Ir, abpy = 2,2''''''''azobispyridine, are reduced to the coordinatively unsaturated compounds [(C5Me5)M(abpy)] via EPR- and UV/VIS-spectroelectrochemically detectable radical intermediates [(C5Me5)MIII(abpy-I)Cl];. Fast-scan cyclic voltammetry allowed us to establish the electrochemical potentials. This stepwise mechanism differs from the two-electron processes observed for analogous systems [(C5Me5)M(N^N)Cl]+/[(C5Me5)M(N^N)] with N^N = 2,2bipyridines, bidiazines or 1,4-diaza-1,3-butadienes. In contrast to cobalt systems like [(C5Me5)Co(bpy)Cl]+ the one-electron reduction does not involve the metal. The role of the abpy ligand as intermediate one-electron storage component for a metal-centered two-electron process is discussed. Further reduction of [(C5Me5)M(abpy)] to [(C5Me5)MII(abpy-II)]- at very negative potentials illustrates the extremely strong ; back donation from the 14 valence electron fragments (C5Me5)M, M = Rh or Ir." .