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Statements

Subject Item
n2:RIV%2F60461373%3A22310%2F06%3A00016996%21RIV07-GA0-22310___
rdf:type
skos:Concept n17:Vysledek
dcterms:description
Pomocí 1H NMR byly stanoveny bariéry rotace aromátu v cis-tetrakarbonyl[(h2-N-allyl-N-allylamino)(4-X-fenyl)carben]chromium(0) (X = MeO, Me, H, Cl, CO2Me and CF3) . Substituted chromium aminocarbene complexes cis-tetracarbonyl[(h2-N-allyl-N-allylamino)(4-X-phenyl)carbene]chromium(0) (X = MeO, Me, H, Cl, CO2Me and CF3) were prepared by the reaction of the corresponding N,N-diallylamides with Na2Cr(CO)5 and Me3SiCl. Using dynamic NMR, the rotational barrier of the aryl ring in these complexes was established. The obtained values are higher for the complexes bearing electron-acceptors compared to those bearing donor substituents and correspond with the Hammett equation. This indicates that the restricted rotation of aryl ring in the chromium aminocarbene complexes is a balance between steric and conjugation effects; while the former increases the barrier, the latter decreases it by stabilizing of the transition state of the rotation. This finding is compatible with the fact, that in the related cis-tetracarbonyl[(N-alkyl-h2-N-allylamino)(phenyl)carbene]chromium(0) complexes (alkyl = Me, Et and i-Pr) the rotational barrier grows steadily with the growing steric deman Substituted chromium aminocarbene complexes cis-tetracarbonyl[(h2-N-allyl-N-allylamino)(4-X-phenyl)carbene]chromium(0) (X = MeO, Me, H, Cl, CO2Me and CF3) were prepared by the reaction of the corresponding N,N-diallylamides with Na2Cr(CO)5 and Me3SiCl. Using dynamic NMR, the rotational barrier of the aryl ring in these complexes was established. The obtained values are higher for the complexes bearing electron-acceptors compared to those bearing donor substituents and correspond with the Hammett equation. This indicates that the restricted rotation of aryl ring in the chromium aminocarbene complexes is a balance between steric and conjugation effects; while the former increases the barrier, the latter decreases it by stabilizing of the transition state of the rotation. This finding is compatible with the fact, that in the related cis-tetracarbonyl[(N-alkyl-h2-N-allylamino)(phenyl)carbene]chromium(0) complexes (alkyl = Me, Et and i-Pr) the rotational barrier grows steadily with the growing steric deman
dcterms:title
Studium původu bráněné rotace aromátu v aminokarbenových komplexech chromu nesoucích aromatický kruh vázaný na karbenový atom uhlíku. Study of the Origin of the Hindered Rotation of an Aryl Ring in the Chromium Aminocarbene Complexes Bearing Aromatic Ring Attached to the Carbene Carbon Atom. Study of the Origin of the Hindered Rotation of an Aryl Ring in the Chromium Aminocarbene Complexes Bearing Aromatic Ring Attached to the Carbene Carbon Atom.
skos:prefLabel
Study of the Origin of the Hindered Rotation of an Aryl Ring in the Chromium Aminocarbene Complexes Bearing Aromatic Ring Attached to the Carbene Carbon Atom. Study of the Origin of the Hindered Rotation of an Aryl Ring in the Chromium Aminocarbene Complexes Bearing Aromatic Ring Attached to the Carbene Carbon Atom. Studium původu bráněné rotace aromátu v aminokarbenových komplexech chromu nesoucích aromatický kruh vázaný na karbenový atom uhlíku.
skos:notation
RIV/60461373:22310/06:00016996!RIV07-GA0-22310___
n3:strany
5540-5548
n3:aktivita
n13:P
n3:aktivity
P(GA203/00/1240), P(GA203/04/0487)
n3:cisloPeriodika
23
n3:dodaniDat
n18:2007
n3:domaciTvurceVysledku
n11:6702198 n11:7241852 n11:8605580 n11:5078008
n3:druhVysledku
n16:J
n3:duvernostUdaju
n10:S
n3:entitaPredkladatele
n6:predkladatel
n3:idSjednocenehoVysledku
502322
n3:idVysledku
RIV/60461373:22310/06:00016996
n3:jazykVysledku
n15:eng
n3:klicovaSlova
Chromium; Aminocarbenes; rotation barrier
n3:klicoveSlovo
n12:Chromium n12:rotation%20barrier n12:Aminocarbenes
n3:kodStatuVydavatele
US - Spojené státy americké
n3:kontrolniKodProRIV
[ADA8448E9886]
n3:nazevZdroje
Organometallics
n3:obor
n7:CC
n3:pocetDomacichTvurcuVysledku
4
n3:pocetTvurcuVysledku
5
n3:projekt
n14:GA203%2F00%2F1240 n14:GA203%2F04%2F0487
n3:rokUplatneniVysledku
n18:2006
n3:svazekPeriodika
25
n3:tvurceVysledku
Černý, Jiří Dvořák, Dalimil Tobrman, Tomáš Meca, Luděk Dvořáková, Hana
s:issn
0276-7333
s:numberOfPages
9
n8:organizacniJednotka
22310