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Statements

Subject Item
n2:RIV%2F61388955%3A_____%2F12%3A00380854%21RIV13-GA0-61388955
rdf:type
skos:Concept n18:Vysledek
dcterms:description
The series of half-sandwich metallocenes of group 4 metals containing the C,N-chelating ligand (η5-C5Me4R)MCl2(C6H4CH2NMe2-κ2C,N) (M = Ti(1), Zr(2), Hf(3); R = Me(C), H(D)) were prepared by reacting the corresponding pentamethyl- and tetramethyl-substituted cyclopentadienylmetal trichlorides (η5-C5Me4R)MCl3 (M = Ti(1), Zr(2), Hf(3); R = Me(A), H(B)) with 2-[(dimethylamino)methyl]phenyl lithium. The X-ray crystal structure analysis of 1C–3C showed that they are isostructural/isomorphous containing two pairs of enantiomers in a P21/c unit cell, whereas crystals of 2D and 3D contained only one enantiomer in a P212121 unit cell. The presence of enantiomers in solution was resolved in variable temperature 1H NMR spectra below the temperature of signal coalescence. The transition state for interconversion of the two enantiomers for 1C was identified by DFT results to be on a 2nd order saddle point. Synthesis of η5-tetramethylcyclopentadienylmetal trichlorides 2B and 3B and their tetrameric and dimeric crystal structures are also reported. The series of half-sandwich metallocenes of group 4 metals containing the C,N-chelating ligand (η5-C5Me4R)MCl2(C6H4CH2NMe2-κ2C,N) (M = Ti(1), Zr(2), Hf(3); R = Me(C), H(D)) were prepared by reacting the corresponding pentamethyl- and tetramethyl-substituted cyclopentadienylmetal trichlorides (η5-C5Me4R)MCl3 (M = Ti(1), Zr(2), Hf(3); R = Me(A), H(B)) with 2-[(dimethylamino)methyl]phenyl lithium. The X-ray crystal structure analysis of 1C–3C showed that they are isostructural/isomorphous containing two pairs of enantiomers in a P21/c unit cell, whereas crystals of 2D and 3D contained only one enantiomer in a P212121 unit cell. The presence of enantiomers in solution was resolved in variable temperature 1H NMR spectra below the temperature of signal coalescence. The transition state for interconversion of the two enantiomers for 1C was identified by DFT results to be on a 2nd order saddle point. Synthesis of η5-tetramethylcyclopentadienylmetal trichlorides 2B and 3B and their tetrameric and dimeric crystal structures are also reported.
dcterms:title
Synthesis, structure, and fluxional behaviour of highly-substituted group 4 cyclopentadienyl arylaminate complexes Synthesis, structure, and fluxional behaviour of highly-substituted group 4 cyclopentadienyl arylaminate complexes
skos:prefLabel
Synthesis, structure, and fluxional behaviour of highly-substituted group 4 cyclopentadienyl arylaminate complexes Synthesis, structure, and fluxional behaviour of highly-substituted group 4 cyclopentadienyl arylaminate complexes
skos:notation
RIV/61388955:_____/12:00380854!RIV13-GA0-61388955
n18:predkladatel
n19:ico%3A61388955
n3:aktivita
n9:Z n9:I n9:S n9:P
n3:aktivity
I, P(GAP106/10/0924), S, Z(AV0Z40400503)
n3:cisloPeriodika
November
n3:dodaniDat
n10:2013
n3:domaciTvurceVysledku
n4:9689907 n4:6769330 n4:5347440 n4:6327230
n3:druhVysledku
n11:J
n3:duvernostUdaju
n6:S
n3:entitaPredkladatele
n7:predkladatel
n3:idSjednocenehoVysledku
173002
n3:idVysledku
RIV/61388955:_____/12:00380854
n3:jazykVysledku
n16:eng
n3:klicovaSlova
Half-sandwich complexes; Titanium Zirconium; Hafnium
n3:klicoveSlovo
n8:Hafnium n8:Half-sandwich%20complexes n8:Titanium%20Zirconium
n3:kodStatuVydavatele
CH - Švýcarská konfederace
n3:kontrolniKodProRIV
[D1149CF2C5D2]
n3:nazevZdroje
Journal of Organometallic Chemistry
n3:obor
n15:CF
n3:pocetDomacichTvurcuVysledku
4
n3:pocetTvurcuVysledku
7
n3:projekt
n5:GAP106%2F10%2F0924
n3:rokUplatneniVysledku
n10:2012
n3:svazekPeriodika
719
n3:tvurceVysledku
Padělková, Z. Růžička, A. Havlík, A. Horáček, Michal Gyepes, Robert Pinkas, Jiří Lamač, Martin
n3:wos
000310769600011
n3:zamer
n20:AV0Z40400503
s:issn
0022-328X
s:numberOfPages
10
n17:doi
10.1016/j.jorganchem.2012.07.036