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Statements

Subject Item
n2:RIV%2F61388955%3A_____%2F03%3A54030108%21RIV%2F2004%2FAV0%2FA54004%2FN
rdf:type
n5:Vysledek skos:Concept
dcterms: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.
dcterms: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
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
skos:notation
RIV/61388955:_____/03:54030108!RIV/2004/AV0/A54004/N
n4:strany
2240;2244
n4:aktivita
n15:P n15:Z
n4:aktivity
P(GA203/03/0821), Z(AV0Z4040901)
n4:cisloPeriodika
N/A
n4:dodaniDat
n7:2004
n4:domaciTvurceVysledku
n8:3742121
n4:druhVysledku
n13:J
n4:duvernostUdaju
n17:S
n4:entitaPredkladatele
n12:predkladatel
n4:idSjednocenehoVysledku
625426
n4:idVysledku
RIV/61388955:_____/03:54030108
n4:jazykVysledku
n6:eng
n4:klicovaSlova
electrochemical generation; iridium(III) complexes; bridging ligands
n4:klicoveSlovo
n9:iridium%28III%29%20complexes n9:bridging%20ligands n9:electrochemical%20generation
n4:kodStatuVydavatele
US - Spojené státy americké
n4:kontrolniKodProRIV
[EE99408C9ABE]
n4:nazevZdroje
Organometallics
n4:obor
n18:CG
n4:pocetDomacichTvurcuVysledku
1
n4:pocetTvurcuVysledku
4
n4:pocetUcastnikuAkce
0
n4:pocetZahranicnichUcastnikuAkce
0
n4:projekt
n11:GA203%2F03%2F0821
n4:rokUplatneniVysledku
n7:2003
n4:svazekPeriodika
22
n4:tvurceVysledku
Kaim, W. Fiedler, Jan Greulich, S. Reinhardt, R.
n4:zamer
n14:AV0Z4040901
s:issn
0276-7333
s:numberOfPages
5