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

Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F03%3A54030108" target="_blank" >RIV/61388955:_____/03:54030108 - isvavai.cz</a>
Result on the web
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DOI - Digital Object Identifier
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Result language
angličtina
Original language name
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
Original language 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.
Czech name
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Czech description
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Type
J<sub>x</sub> - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)
CEP classification
CG - Electrochemistry
OECD FORD branch
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Project
<a href="/en/project/GA203%2F03%2F0821" target="_blank" >GA203/03/0821: Electron transfer to new supramolecular complexes, large molecules with multiple active centers and ordered structures</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)<br>Z - Vyzkumny zamer (s odkazem do CEZ)

Publication year
2003
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

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