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Statements

Subject Item
n2:RIV%2F61388955%3A_____%2F02%3A54020181%21RIV%2F2003%2FAV0%2FA54003%2FN
rdf:type
n10:Vysledek skos:Concept
dcterms:description
The temperature-dependent intramolecular metal/ligand electron transfer equilibrium (L)Cu-II(Q(2-))reversible arrow(L)Cu-I(Q(.-)) has been quantitatively analyzed by EPR as a function of the non-innocent o-quinonoid ligand Q and of the co-ligand L. Suitable co-ligands were 1-methyl-(2-methylthiomethyl)-1H-benzimidazole and 1-diphenylphosphino-2-dimethylaminoethane (dde) which can tolerate both copper oxidation states. EPR hyperfine data were extracted for a variety of alkyl- and methoxy-substituted o-semiquinones and their copper(l) complexes in solution. A close match of Q and Cu redox orbitals is essential for observing the redox isomer equilibrium which has been similarly reported for aminoxidase enzymes. Efforts to isolate the mixed-ligand compounds from solution failed due to coordination disproportionation. The new [Cu(dde)(2)](ClO4) was structurally characterized with comparable Cu-N and Cu-P distances of 2.24-2.27 Angstrom and a P-Cu-P angle of 142.41(5)degrees. The temperature-dependent intramolecular metal/ligand electron transfer equilibrium (L)Cu-II(Q(2-))reversible arrow(L)Cu-I(Q(.-)) has been quantitatively analyzed by EPR as a function of the non-innocent o-quinonoid ligand Q and of the co-ligand L. Suitable co-ligands were 1-methyl-(2-methylthiomethyl)-1H-benzimidazole and 1-diphenylphosphino-2-dimethylaminoethane (dde) which can tolerate both copper oxidation states. EPR hyperfine data were extracted for a variety of alkyl- and methoxy-substituted o-semiquinones and their copper(l) complexes in solution. A close match of Q and Cu redox orbitals is essential for observing the redox isomer equilibrium which has been similarly reported for aminoxidase enzymes. Efforts to isolate the mixed-ligand compounds from solution failed due to coordination disproportionation. The new [Cu(dde)(2)](ClO4) was structurally characterized with comparable Cu-N and Cu-P distances of 2.24-2.27 Angstrom and a P-Cu-P angle of 142.41(5)degrees.
dcterms:title
Copper Complexes with Non-innocent Ligands: Probing Cu-II/catecholato-Cu-I/o-Semiquinonato Redox Isomer Equilibria with EPR Spectroscopy. Copper Complexes with Non-innocent Ligands: Probing Cu-II/catecholato-Cu-I/o-Semiquinonato Redox Isomer Equilibria with EPR Spectroscopy.
skos:prefLabel
Copper Complexes with Non-innocent Ligands: Probing Cu-II/catecholato-Cu-I/o-Semiquinonato Redox Isomer Equilibria with EPR Spectroscopy. Copper Complexes with Non-innocent Ligands: Probing Cu-II/catecholato-Cu-I/o-Semiquinonato Redox Isomer Equilibria with EPR Spectroscopy.
skos:notation
RIV/61388955:_____/02:54020181!RIV/2003/AV0/A54003/N
n4:strany
163;172
n4:aktivita
n13:Z n13:P
n4:aktivity
P(OC D14.20), Z(AV0Z4040901)
n4:cisloPeriodika
N/A
n4:dodaniDat
n17:2003
n4:domaciTvurceVysledku
n11:3953084
n4:druhVysledku
n14:J
n4:duvernostUdaju
n6:S
n4:entitaPredkladatele
n7:predkladatel
n4:idSjednocenehoVysledku
641774
n4:idVysledku
RIV/61388955:_____/02:54020181
n4:jazykVysledku
n16:eng
n4:klicovaSlova
copper compounds; EPR spectroscopy; quinone ligands
n4:klicoveSlovo
n5:EPR%20spectroscopy n5:copper%20compounds n5:quinone%20ligands
n4:kodStatuVydavatele
CH - Švýcarská konfederace
n4:kontrolniKodProRIV
[FA1824267A2C]
n4:nazevZdroje
Inorganica Chimica Acta
n4:obor
n12:CF
n4:pocetDomacichTvurcuVysledku
1
n4:pocetTvurcuVysledku
4
n4:pocetUcastnikuAkce
0
n4:pocetZahranicnichUcastnikuAkce
0
n4:projekt
n18:OC%20D14.20
n4:rokUplatneniVysledku
n17:2002
n4:svazekPeriodika
337
n4:tvurceVysledku
Záliš, Stanislav Kaim, W. Wanner, M. Knödler, A.
n4:zamer
n15:AV0Z4040901
s:issn
0020-1693
s:numberOfPages
10