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Statements

Subject Item
n2:RIV%2F61388955%3A_____%2F11%3A00358409%21RIV12-GA0-61388955
rdf:type
n11:Vysledek skos:Concept
dcterms:description
Aryloxychloro and bis(aryloxy) titanocenes of general formula L2TiCl2-x(OAr')(x) where L = eta(5)-C5H5 (x = 1 (1) and 2 (2)), L-2 = SiMe2(eta(5)-C5H4)(2) (x = 1 (3) and 2 (4)), and Ar' = 2,6-(CHMe2)(2)C6H3 were prepared by the reaction of corresponding titanocene dichloride with LiOAr' and characterized by spectroscopic methods and compound 3 by single crystal X-ray diffraction analysis. The bulky aryloxy ligand in 1 and 3 exerts a hindered rotation around the Ti-O bond on the H-1 NMR time scale, resulting in its dynamic behavior in CDCl3 solution. Variable temperature NMR measurements proved the rotation barrier in 3 (Delta G(298)(double dagger) = 13.9 +/- 0.3 kcal/mol) to be lower than that in 1 (Delta G(298)(double dagger) = 14.7 +/- 0.2 kcal/mol) as a consequence of the more open titanocene shell in the ansa-structure of 3. Aryloxychloro and bis(aryloxy) titanocenes of general formula L2TiCl2-x(OAr')(x) where L = eta(5)-C5H5 (x = 1 (1) and 2 (2)), L-2 = SiMe2(eta(5)-C5H4)(2) (x = 1 (3) and 2 (4)), and Ar' = 2,6-(CHMe2)(2)C6H3 were prepared by the reaction of corresponding titanocene dichloride with LiOAr' and characterized by spectroscopic methods and compound 3 by single crystal X-ray diffraction analysis. The bulky aryloxy ligand in 1 and 3 exerts a hindered rotation around the Ti-O bond on the H-1 NMR time scale, resulting in its dynamic behavior in CDCl3 solution. Variable temperature NMR measurements proved the rotation barrier in 3 (Delta G(298)(double dagger) = 13.9 +/- 0.3 kcal/mol) to be lower than that in 1 (Delta G(298)(double dagger) = 14.7 +/- 0.2 kcal/mol) as a consequence of the more open titanocene shell in the ansa-structure of 3.
dcterms:title
TITANOCENE AND ansa-TITANOCENE COMPLEXES BEARING 2,6-BIS(ISOPROPYL)PHENOXIDE LIGAND(S). SYNTHESES, CHARACTERIZATION AND USE IN CATALYTIC DEHYDROCOUPLING POLYMERIZATION OF PHENYLSILANE TITANOCENE AND ansa-TITANOCENE COMPLEXES BEARING 2,6-BIS(ISOPROPYL)PHENOXIDE LIGAND(S). SYNTHESES, CHARACTERIZATION AND USE IN CATALYTIC DEHYDROCOUPLING POLYMERIZATION OF PHENYLSILANE
skos:prefLabel
TITANOCENE AND ansa-TITANOCENE COMPLEXES BEARING 2,6-BIS(ISOPROPYL)PHENOXIDE LIGAND(S). SYNTHESES, CHARACTERIZATION AND USE IN CATALYTIC DEHYDROCOUPLING POLYMERIZATION OF PHENYLSILANE TITANOCENE AND ansa-TITANOCENE COMPLEXES BEARING 2,6-BIS(ISOPROPYL)PHENOXIDE LIGAND(S). SYNTHESES, CHARACTERIZATION AND USE IN CATALYTIC DEHYDROCOUPLING POLYMERIZATION OF PHENYLSILANE
skos:notation
RIV/61388955:_____/11:00358409!RIV12-GA0-61388955
n11:predkladatel
n12:ico%3A61388955
n4:aktivita
n14:Z n14:P
n4:aktivity
P(GA203/09/1574), P(KAN100400701), P(LC06070), Z(AV0Z40400503), Z(AV0Z40720504), Z(MSM0021620857), Z(MSM6046137302)
n4:cisloPeriodika
1
n4:dodaniDat
n5:2012
n4:domaciTvurceVysledku
n10:7763743 n10:6327230 n10:9689907
n4:druhVysledku
n17:J
n4:duvernostUdaju
n6:S
n4:entitaPredkladatele
n9:predkladatel
n4:idSjednocenehoVysledku
235432
n4:idVysledku
RIV/61388955:_____/11:00358409
n4:jazykVysledku
n19:eng
n4:klicovaSlova
titatium; metallocenes; polymerization
n4:klicoveSlovo
n13:metallocenes n13:titatium n13:polymerization
n4:kodStatuVydavatele
CZ - Česká republika
n4:kontrolniKodProRIV
[994F3621FCF9]
n4:nazevZdroje
Collection of Czechoslovak Chemical Communications
n4:obor
n8:CF
n4:pocetDomacichTvurcuVysledku
3
n4:pocetTvurcuVysledku
6
n4:projekt
n15:GA203%2F09%2F1574 n15:LC06070 n15:KAN100400701
n4:rokUplatneniVysledku
n5:2011
n4:svazekPeriodika
76
n4:tvurceVysledku
Merna, J. Pinkas, Jiří Sýkora, Jan Gyepes, R. Horáček, Michal Kubišta, Jiří
n4:wos
000286069600007
n4:zamer
n7:AV0Z40400503 n7:AV0Z40720504 n7:MSM0021620857 n7:MSM6046137302
s:issn
0010-0765
s:numberOfPages
20
n20:doi
10.1135/cccc2010133