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Statements

Subject Item
n2:RIV%2F61388955%3A_____%2F11%3A00371365%21RIV12-GA0-61388955
rdf:type
n19:Vysledek skos:Concept
dcterms:description
Thermolysis of [TiMe(2){eta(5)-C(5)Me(4)(CH(2)CH(2)CH=CH(2))}(2)] (1) in toluene at 120 C for 4 h resulted in the formation of the cyclopentadiene ring-tethered titanacyclobutane [Ti(IV){eta(5)-C(5)Me(4)CH(2)CH(2)CH(kappa-CH)}(2)CH(2)] (2) in virtually quantitative yields. Thermolysis in an NMR tube at 100 C revealed that initial elimination of methane is followed by addition of one 3-butenyl double bond to a titanocene methylidene moiety. The formed titanacyclobutane intermediate [Ti{eta(5)-C(5)Me(4)(CH(2)CH(2)CH=CH(2))} {eta(5)-C(5)Me(4)CH(2)CH(2)CH (kappa-CH)CH(2)CH(2)-(kappa-CH(2))}] (4) then underwent a metathesis reaction with the pendant 3-butenyl to give 2 and free ethene. Cleavage of Ti-C bonds of 2 with HCl afforded stable ansa-[TiCl(2){eta(5)-C(5)Me(4)(CH(2))(7)eta(5))-C(5)Me(4)}] (3). Sunlight photolysis of 1 gave rise to the cyclopentadiene ring-tethered titanacyclopentane [Ti(IV){eta(5)-C(5)Me(4)(CH(2)CH(2)CH(kappa-CH)CH(2)}(2)] (5), the known product of cycloaddition reactions following the removal of chlorine atoms from [TiCl(2){eta(5)-C(5)Me(4)(CH(2)CH(2)CH=CH(2))}(2)] with magnesium (as found by Horaeek, M. et al. Chem. Eur. J. 2000, 6, 2397). Thermolysis of [TiMe(2){eta(5)-C(5)Me(4)(CH(2)CH(2)CH=CH(2))}(2)] (1) in toluene at 120 C for 4 h resulted in the formation of the cyclopentadiene ring-tethered titanacyclobutane [Ti(IV){eta(5)-C(5)Me(4)CH(2)CH(2)CH(kappa-CH)}(2)CH(2)] (2) in virtually quantitative yields. Thermolysis in an NMR tube at 100 C revealed that initial elimination of methane is followed by addition of one 3-butenyl double bond to a titanocene methylidene moiety. The formed titanacyclobutane intermediate [Ti{eta(5)-C(5)Me(4)(CH(2)CH(2)CH=CH(2))} {eta(5)-C(5)Me(4)CH(2)CH(2)CH (kappa-CH)CH(2)CH(2)-(kappa-CH(2))}] (4) then underwent a metathesis reaction with the pendant 3-butenyl to give 2 and free ethene. Cleavage of Ti-C bonds of 2 with HCl afforded stable ansa-[TiCl(2){eta(5)-C(5)Me(4)(CH(2))(7)eta(5))-C(5)Me(4)}] (3). Sunlight photolysis of 1 gave rise to the cyclopentadiene ring-tethered titanacyclopentane [Ti(IV){eta(5)-C(5)Me(4)(CH(2)CH(2)CH(kappa-CH)CH(2)}(2)] (5), the known product of cycloaddition reactions following the removal of chlorine atoms from [TiCl(2){eta(5)-C(5)Me(4)(CH(2)CH(2)CH=CH(2))}(2)] with magnesium (as found by Horaeek, M. et al. Chem. Eur. J. 2000, 6, 2397).
dcterms:title
Ethene Elimination during Thermolysis of Bis(3-butenyltetramethylcyclopentadienyl)dimethyltitanium Ethene Elimination during Thermolysis of Bis(3-butenyltetramethylcyclopentadienyl)dimethyltitanium
skos:prefLabel
Ethene Elimination during Thermolysis of Bis(3-butenyltetramethylcyclopentadienyl)dimethyltitanium Ethene Elimination during Thermolysis of Bis(3-butenyltetramethylcyclopentadienyl)dimethyltitanium
skos:notation
RIV/61388955:_____/11:00371365!RIV12-GA0-61388955
n19:predkladatel
n20:ico%3A61388955
n3:aktivita
n13:P n13:Z
n3:aktivity
P(GP203/09/P276), P(IAA400400708), P(LC06070), Z(AV0Z40400503)
n3:cisloPeriodika
9
n3:dodaniDat
n5:2012
n3:domaciTvurceVysledku
n4:9689907 n4:7277962 n4:6327230 n4:7763743
n3:druhVysledku
n14:J
n3:duvernostUdaju
n17:S
n3:entitaPredkladatele
n12:predkladatel
n3:idSjednocenehoVysledku
198025
n3:idVysledku
RIV/61388955:_____/11:00371365
n3:jazykVysledku
n8:eng
n3:klicovaSlova
TITANIUM COMPOUNDS (ETA-5-C5ME5)2TIR; OLEFIN METATHESIS REACTION; TITANOCENE DICHLORIDES
n3:klicoveSlovo
n7:OLEFIN%20METATHESIS%20REACTION n7:TITANIUM%20COMPOUNDS%20%28ETA-5-C5ME5%292TIR n7:TITANOCENE%20DICHLORIDES
n3:kodStatuVydavatele
US - Spojené státy americké
n3:kontrolniKodProRIV
[A06CF4B9A231]
n3:nazevZdroje
Organometallics
n3:obor
n9:CF
n3:pocetDomacichTvurcuVysledku
4
n3:pocetTvurcuVysledku
5
n3:projekt
n11:LC06070 n11:GP203%2F09%2FP276 n11:IAA400400708
n3:rokUplatneniVysledku
n5:2011
n3:svazekPeriodika
30
n3:tvurceVysledku
Pinkas, Jiří Mach, Karel Gyepes, R. Horáček, Michal Kubišta, Jiří
n3:wos
000290001900018
n3:zamer
n16:AV0Z40400503
s:issn
0276-7333
s:numberOfPages
6
n18:doi
10.1021/om2001487