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Statements

Subject Item
n2:RIV%2F60461373%3A22310%2F12%3A43893038%21RIV13-GA0-22310___
rdf:type
skos:Concept n12:Vysledek
dcterms:description
A series of fluorous silver complexes bearing two fluorous NHC ligands was synthesized from bis(polyfluoroalkylated) or bis(polyfluoropolyoxa-alkylated) imidazolium salts and silver oxide in acetonitrile. The starting salts were prepared either under conventional conditions in two steps via polyfluoroalkylated imidazoles or preferably directly from imidazole and the respective polyfluoroalkyl triflates or polyfluoropolyoxaalkyl nonaflates bearing a nonfluorinated ethylene or methylene spacer. Surprisingly, striking differences in fluorophilicity were observed for both starting imidazolium salts and target Ag?NHC complexes depending on the type of polyfluorinated chains. While the complexes bearing a polyfluoroalkyl ponytail displayed moderate fluorophilicities f i in the range of 0.9?1.8, the presence of fluorinated polyether chains resulted in much higher fluorophilicity reaching for unbranched polyethers values as high as 3.2 with excellent solubility in perfluorinated solvents. For the explanation, DFT calculations on the model imidazolium salts showed that, in contrast to polyfluoroalkyl ponytails pointing out of the imidazolium rings, dominant conformation of the polyfluoropolyether chain is able to shield fluorophobic counteranions against the perfluorinated environment, minimizing thus fluorophobic interactions. We also employed DFT calculations for the confirmation of the higher flexibility of perfluoropolyether chains compared with perfluoroalkyl chains, scanning the energy content of two model compounds,perfluorohexane and perfluoro-3-oxahexane, on their C3?C4 or O?C3 torsion angle. A series of fluorous silver complexes bearing two fluorous NHC ligands was synthesized from bis(polyfluoroalkylated) or bis(polyfluoropolyoxa-alkylated) imidazolium salts and silver oxide in acetonitrile. The starting salts were prepared either under conventional conditions in two steps via polyfluoroalkylated imidazoles or preferably directly from imidazole and the respective polyfluoroalkyl triflates or polyfluoropolyoxaalkyl nonaflates bearing a nonfluorinated ethylene or methylene spacer. Surprisingly, striking differences in fluorophilicity were observed for both starting imidazolium salts and target Ag?NHC complexes depending on the type of polyfluorinated chains. While the complexes bearing a polyfluoroalkyl ponytail displayed moderate fluorophilicities f i in the range of 0.9?1.8, the presence of fluorinated polyether chains resulted in much higher fluorophilicity reaching for unbranched polyethers values as high as 3.2 with excellent solubility in perfluorinated solvents. For the explanation, DFT calculations on the model imidazolium salts showed that, in contrast to polyfluoroalkyl ponytails pointing out of the imidazolium rings, dominant conformation of the polyfluoropolyether chain is able to shield fluorophobic counteranions against the perfluorinated environment, minimizing thus fluorophobic interactions. We also employed DFT calculations for the confirmation of the higher flexibility of perfluoropolyether chains compared with perfluoroalkyl chains, scanning the energy content of two model compounds,perfluorohexane and perfluoro-3-oxahexane, on their C3?C4 or O?C3 torsion angle.
dcterms:title
Ag Complexes of NHC Ligands Bearing Polyfluoroalkyl and/or Polyfluoropolyalkoxy Ponytails. Why Are Polyethers More Fluorous Than Alkyls? Ag Complexes of NHC Ligands Bearing Polyfluoroalkyl and/or Polyfluoropolyalkoxy Ponytails. Why Are Polyethers More Fluorous Than Alkyls?
skos:prefLabel
Ag Complexes of NHC Ligands Bearing Polyfluoroalkyl and/or Polyfluoropolyalkoxy Ponytails. Why Are Polyethers More Fluorous Than Alkyls? Ag Complexes of NHC Ligands Bearing Polyfluoroalkyl and/or Polyfluoropolyalkoxy Ponytails. Why Are Polyethers More Fluorous Than Alkyls?
skos:notation
RIV/60461373:22310/12:43893038!RIV13-GA0-22310___
n12:predkladatel
n13:orjk%3A22310
n3:aktivita
n11:V n11:Z n11:P
n3:aktivity
P(GAP207/10/1533), P(LC06070), V, Z(AV0Z40550506), Z(MSM6046137301)
n3:cisloPeriodika
2
n3:dodaniDat
n18:2013
n3:domaciTvurceVysledku
n17:9539379 n17:8596492 n17:6663060 n17:4589181
n3:druhVysledku
n21:J
n3:duvernostUdaju
n6:S
n3:entitaPredkladatele
n20:predkladatel
n3:idSjednocenehoVysledku
121288
n3:idVysledku
RIV/60461373:22310/12:43893038
n3:jazykVysledku
n15:eng
n3:klicovaSlova
DFT; perfluoropolyether; polyfluoropolyalkoxy; polyfluoroalkyl; fluorous; NHC ligand; Ag complex
n3:klicoveSlovo
n7:fluorous n7:perfluoropolyether n7:DFT n7:polyfluoroalkyl n7:polyfluoropolyalkoxy n7:Ag%20complex n7:NHC%20ligand
n3:kodStatuVydavatele
US - Spojené státy americké
n3:kontrolniKodProRIV
[218F3562747C]
n3:nazevZdroje
Organometallics
n3:obor
n8:CC
n3:pocetDomacichTvurcuVysledku
4
n3:pocetTvurcuVysledku
8
n3:projekt
n10:GAP207%2F10%2F1533 n10:LC06070
n3:rokUplatneniVysledku
n18:2012
n3:svazekPeriodika
31
n3:tvurceVysledku
Cvačka, Josef Březinová, Anna Kvíčalová, Magdalena Skalický, Martin Rybáčková, Markéta Kvíčala, Jaroslav Skalická, Veronika Paterová, Jana
n3:wos
000300738800033
n3:zamer
n4:AV0Z40550506 n4:MSM6046137301
s:issn
0276-7333
s:numberOfPages
9
n16:doi
10.1021/om201062c
n14:organizacniJednotka
22310