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

Kód výsledku v 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>

Výsledek na webu

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DOI - Digital Object Identifier

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Jazyk výsledku

angličtina

Název v původním jazyce

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

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

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

Popis výsledku anglicky

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.

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CG - Elektrochemie

OECD FORD obor

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Projekt

<a href="/cs/project/GA203%2F03%2F0821" target="_blank" >GA203/03/0821: Přenos elektronu v supramolekulárních komplexech, velkých molekulách s více aktivními centry a v organizovaných strukturách</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)<br>Z - Vyzkumny zamer (s odkazem do CEZ)

Rok uplatnění

2003

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Organometallics

ISSN

0276-7333

e-ISSN

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Svazek periodika

22

Číslo periodika v rámci svazku

N/A

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

5

Strana od-do

2240-2244

Kód UT WoS článku

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EID výsledku v databázi Scopus

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