About: 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     Goto   Sponge   NotDistinct   Permalink

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Description
  • 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.
  • 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)
Title
  • 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
  • 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)
skos:prefLabel
  • 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
  • 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)
skos:notation
  • RIV/61388955:_____/03:54030108!RIV/2004/AV0/A54004/N
http://linked.open.../vavai/riv/strany
  • 2240;2244
http://linked.open...avai/riv/aktivita
http://linked.open...avai/riv/aktivity
  • P(GA203/03/0821), Z(AV0Z4040901)
http://linked.open...iv/cisloPeriodika
  • N/A
http://linked.open...vai/riv/dodaniDat
http://linked.open...aciTvurceVysledku
http://linked.open.../riv/druhVysledku
http://linked.open...iv/duvernostUdaju
http://linked.open...titaPredkladatele
http://linked.open...dnocenehoVysledku
  • 625426
http://linked.open...ai/riv/idVysledku
  • RIV/61388955:_____/03:54030108
http://linked.open...riv/jazykVysledku
http://linked.open.../riv/klicovaSlova
  • electrochemical generation; iridium(III) complexes; bridging ligands (en)
http://linked.open.../riv/klicoveSlovo
http://linked.open...odStatuVydavatele
  • US - Spojené státy americké
http://linked.open...ontrolniKodProRIV
  • [EE99408C9ABE]
http://linked.open...i/riv/nazevZdroje
  • Organometallics
http://linked.open...in/vavai/riv/obor
http://linked.open...ichTvurcuVysledku
http://linked.open...cetTvurcuVysledku
http://linked.open...ocetUcastnikuAkce
http://linked.open...nichUcastnikuAkce
http://linked.open...vavai/riv/projekt
http://linked.open...UplatneniVysledku
http://linked.open...v/svazekPeriodika
  • 22
http://linked.open...iv/tvurceVysledku
  • Fiedler, Jan
  • Kaim, W.
  • Greulich, S.
  • Reinhardt, R.
http://linked.open...n/vavai/riv/zamer
issn
  • 0276-7333
number of pages
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