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Statements

Subject Item
n2:RIV%2F61388955%3A_____%2F14%3A00434726%21RIV15-AV0-61388955
rdf:type
skos:Concept n10:Vysledek
dcterms:description
The complex cations [Cu(dippf)(DML)](+) ([1](+)) and [Cu(dppf)(DML)](+) ([2](+)), where dippf = 1,1'-bis(diisopropylphosphino)ferrocene, dppf = 1,1'-bis(diphenylphosphino)ferrocene, and DML = 1,3-dimethyllumazine, were prepared and crystallized as BF4- or PF6- salts. Structure determinations of the tetrafluoroborates revealed asymmetric O-4,N-5 chelation of DML to copper(I) with longer Cu-O bonds of about 2.25 angstrom. Reversible oxidation to [1](2+) and [2](2+) proceeds at the ferrocene units, while reduction leads to the neutral radical complexes [1] and [2] with the unpaired electron localized on the DML ligand. The occurrence of two voltammetric steps for the one-electron-reduction process is attributed to a two-species equilibrium caused by the hemilabile coordination of DML. Electrochemical and spectroelectrochemical measurements (UV-vis, IR) reveal increased coordination lability of the reduced complexes and their slow fragmentation. The complex cations [Cu(dippf)(DML)](+) ([1](+)) and [Cu(dppf)(DML)](+) ([2](+)), where dippf = 1,1'-bis(diisopropylphosphino)ferrocene, dppf = 1,1'-bis(diphenylphosphino)ferrocene, and DML = 1,3-dimethyllumazine, were prepared and crystallized as BF4- or PF6- salts. Structure determinations of the tetrafluoroborates revealed asymmetric O-4,N-5 chelation of DML to copper(I) with longer Cu-O bonds of about 2.25 angstrom. Reversible oxidation to [1](2+) and [2](2+) proceeds at the ferrocene units, while reduction leads to the neutral radical complexes [1] and [2] with the unpaired electron localized on the DML ligand. The occurrence of two voltammetric steps for the one-electron-reduction process is attributed to a two-species equilibrium caused by the hemilabile coordination of DML. Electrochemical and spectroelectrochemical measurements (UV-vis, IR) reveal increased coordination lability of the reduced complexes and their slow fragmentation.
dcterms:title
Electrochemical Evidence for Hemilabile Coordination of 1,3-Dimethyllumazine to [1,1 '-Bis(diorganophosphino)ferrocene]copper(I) Electrochemical Evidence for Hemilabile Coordination of 1,3-Dimethyllumazine to [1,1 '-Bis(diorganophosphino)ferrocene]copper(I)
skos:prefLabel
Electrochemical Evidence for Hemilabile Coordination of 1,3-Dimethyllumazine to [1,1 '-Bis(diorganophosphino)ferrocene]copper(I) Electrochemical Evidence for Hemilabile Coordination of 1,3-Dimethyllumazine to [1,1 '-Bis(diorganophosphino)ferrocene]copper(I)
skos:notation
RIV/61388955:_____/14:00434726!RIV15-AV0-61388955
n3:aktivita
n9:I n9:P
n3:aktivity
I, P(LD14129)
n3:cisloPeriodika
18
n3:dodaniDat
n4:2015
n3:domaciTvurceVysledku
n16:3742121
n3:druhVysledku
n13:J
n3:duvernostUdaju
n6:S
n3:entitaPredkladatele
n11:predkladatel
n3:idSjednocenehoVysledku
14111
n3:idVysledku
RIV/61388955:_____/14:00434726
n3:jazykVysledku
n18:eng
n3:klicovaSlova
electrochemistry; metal complexes; crystal structure
n3:klicoveSlovo
n8:metal%20complexes n8:electrochemistry n8:crystal%20structure
n3:kodStatuVydavatele
US - Spojené státy americké
n3:kontrolniKodProRIV
[0903D347C97B]
n3:nazevZdroje
Organometallics
n3:obor
n17:CG
n3:pocetDomacichTvurcuVysledku
1
n3:pocetTvurcuVysledku
6
n3:projekt
n7:LD14129
n3:rokUplatneniVysledku
n4:2014
n3:svazekPeriodika
33
n3:tvurceVysledku
Fiedler, Jan Strobel, S. Mobin, S. M. Kaim, W. Jana, R. Sarkar, B.
n3:wos
000342180800026
s:issn
0276-7333
s:numberOfPages
8
n12:doi
10.1021/om500039a