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Statements

Subject Item
n2:RIV%2F61388955%3A_____%2F07%3A00084868%21RIV08-MSM-61388955
rdf:type
n13:Vysledek skos:Concept
dcterms:description
Komplexy (.mu.3-L1/L2)[Ru(acac)2]3, acac- = 2,4-pentanedionato, L1 = 2,3,8,9,14,15-hexachlorodichinoxalino[2,3-:2',3'-c] fenazin a L2 = 2,3,8,9,14,15-hexamethyldichinoxalino[2,3-:2',3'-c] fenazin, podléhají postupné jednoelektronové oxidaci zahrnující celkově tři elektrony a postupné jednoelektronové redukci se třemi (L2) nebo čtyřmi elektrony (L1). Všechny reversibilně dostupné stavy byly charakterizovány UV-VIS-NIR spektroelektrochemií. Oxidace vede k meziproduktům se smíšenou valencí {(.mu.3-L)[Ru(acac)2]3}+ a {(.mu.3-L)[Ru(acac)2]3}2+, z nichž kombinace RuIIIRuIIRuII vykazují vyšší komproporcionační konstanty Kc než RuIIIRuIIIRuII stavy – na rozdíl od dříve popsaných nesubstituovaných mateřských systémů {(.mu.3-L3)[Ru(acac)2]3}+/2+/, L3 = dichinoxalino[2,3-:2´,3´-c] fenazin. Pro meziprodukty se smíšenou valencí nebyl pozorován v blízké infračervené oblasti žádný zřetelný absorbční pás přenosu náboje. The complexes (.mu.3-L1/L2)[Ru(acac)2]3, acac- = 2,4-pentanedionato, L1 = 2,3,8,9,14,15-hexachlorodiquinoxalino[2,3-a:2’,3’-c]phenazine and L2 = 2,3,8,9,14,15-hexamethyldiquinoxalino[2,3-a:2’,3’-c]phenazine, undergo stepwise one-electron oxidation involving a total of three electrons and stepwise one-electron reduction with three (L2) or four electrons (L1). All reversibly accessible states were characterized by UV–Vis–NIR spectroelectrochemistry. Oxidation leads to mixed-valent intermediates {(.mu.3-L)[Ru(acac)2]3}+ and {(.mu.3-L)[Ru(acac)2]3}2+ of which the RuIIIRuIIRuII combinations exhibit higher comproportionation constants Kc than the RuIIIRuIIIRuII states – in contrast to a previous report for the unsubstituted parent systems {(.mu.3-L3)[Ru(acac)2]3}+/2+, L3 = diquinoxalino[2,3-a:2´,3´-c]phenazine. No conspicuous inter-valence charge transfer absorptions were observed for the mixed-valent intermediates in the visible to near-infrared regions. The complexes (.mu.3-L1/L2)[Ru(acac)2]3, acac- = 2,4-pentanedionato, L1 = 2,3,8,9,14,15-hexachlorodiquinoxalino[2,3-a:2’,3’-c]phenazine and L2 = 2,3,8,9,14,15-hexamethyldiquinoxalino[2,3-a:2’,3’-c]phenazine, undergo stepwise one-electron oxidation involving a total of three electrons and stepwise one-electron reduction with three (L2) or four electrons (L1). All reversibly accessible states were characterized by UV–Vis–NIR spectroelectrochemistry. Oxidation leads to mixed-valent intermediates {(.mu.3-L)[Ru(acac)2]3}+ and {(.mu.3-L)[Ru(acac)2]3}2+ of which the RuIIIRuIIRuII combinations exhibit higher comproportionation constants Kc than the RuIIIRuIIIRuII states – in contrast to a previous report for the unsubstituted parent systems {(.mu.3-L3)[Ru(acac)2]3}+/2+, L3 = diquinoxalino[2,3-a:2´,3´-c]phenazine. No conspicuous inter-valence charge transfer absorptions were observed for the mixed-valent intermediates in the visible to near-infrared regions.
dcterms:title
Multiple one-electron oxidation and reduction of trinuclear bis(2,4-pentanedionato)ruthenium complexes with substituted diquinoxalino[2,3-a:2´,3´-c]phenazine ligands Multiple one-electron oxidation and reduction of trinuclear bis(2,4-pentanedionato)ruthenium complexes with substituted diquinoxalino[2,3-a:2´,3´-c]phenazine ligands Vícenásobná jednoelektronová oxidace a redukce tříjaderných bis(1,3-pentanedionato)rutheniových komplexů se substituovanými dichinoxalin[2,3-: 2´,3´-c] fenaziny
skos:prefLabel
Vícenásobná jednoelektronová oxidace a redukce tříjaderných bis(1,3-pentanedionato)rutheniových komplexů se substituovanými dichinoxalin[2,3-: 2´,3´-c] fenaziny Multiple one-electron oxidation and reduction of trinuclear bis(2,4-pentanedionato)ruthenium complexes with substituted diquinoxalino[2,3-a:2´,3´-c]phenazine ligands Multiple one-electron oxidation and reduction of trinuclear bis(2,4-pentanedionato)ruthenium complexes with substituted diquinoxalino[2,3-a:2´,3´-c]phenazine ligands
skos:notation
RIV/61388955:_____/07:00084868!RIV08-MSM-61388955
n3:strany
3409;3418
n3:aktivita
n4:Z n4:P
n3:aktivity
P(1P05OC068), P(LC510), Z(AV0Z40400503)
n3:cisloPeriodika
13
n3:dodaniDat
n9:2008
n3:domaciTvurceVysledku
n17:3742121
n3:druhVysledku
n15:J
n3:duvernostUdaju
n18:S
n3:entitaPredkladatele
n7:predkladatel
n3:idSjednocenehoVysledku
435697
n3:idVysledku
RIV/61388955:_____/07:00084868
n3:jazykVysledku
n14:eng
n3:klicovaSlova
DFT calculation; EPR; radical complexes; electrochemistry
n3:klicoveSlovo
n10:radical%20complexes n10:EPR n10:DFT%20calculation n10:electrochemistry
n3:kodStatuVydavatele
NL - Nizozemsko
n3:kontrolniKodProRIV
[90EC8C2478A8]
n3:nazevZdroje
Polyhedron
n3:obor
n16:CG
n3:pocetDomacichTvurcuVysledku
1
n3:pocetTvurcuVysledku
7
n3:projekt
n8:LC510 n8:1P05OC068
n3:rokUplatneniVysledku
n9:2007
n3:svazekPeriodika
26
n3:tvurceVysledku
Sarkar, B. Patil, M. P. Ghumaan, S. Kaim, W. Lahiri, G. K. Sunoj, R. B. Fiedler, Jan
n3:zamer
n11:AV0Z40400503
s:issn
0277-5387
s:numberOfPages
10