About: Ethene Elimination during Thermolysis of Bis(3-butenyltetramethylcyclopentadienyl)dimethyltitanium

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About: Ethene Elimination during Thermolysis of Bis(3-butenyltetramethylcyclopentadienyl)dimethyltitanium Goto Sponge NotDistinct Permalink

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rdf:type	skos:Concept http://linked.opendata.cz/ontology/domain/vavai/Vysledek
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). (en)
Title	Ethene Elimination during Thermolysis of Bis(3-butenyltetramethylcyclopentadienyl)dimethyltitanium Ethene Elimination during Thermolysis of Bis(3-butenyltetramethylcyclopentadienyl)dimethyltitanium (en)
skos:prefLabel	Ethene Elimination during Thermolysis of Bis(3-butenyltetramethylcyclopentadienyl)dimethyltitanium Ethene Elimination during Thermolysis of Bis(3-butenyltetramethylcyclopentadienyl)dimethyltitanium (en)
skos:notation	RIV/61388955:_____/11:00371365!RIV12-GA0-61388955
http://linked.open...avai/riv/aktivita	P Z
http://linked.open...avai/riv/aktivity	P(GP203/09/P276), P(IAA400400708), P(LC06070), Z(AV0Z40400503)
http://linked.open...iv/cisloPeriodika	9
http://linked.open...vai/riv/dodaniDat	2012
http://linked.open...aciTvurceVysledku	Horáček, Michal Mach, Karel Kubišta, Jiří Pinkas, Jiří
http://linked.open.../riv/druhVysledku	J - Článek v odborném periodiku
http://linked.open...iv/duvernostUdaju	S - Úplné a pravdivé údaje nepodléhající ochraně podle zvláštních právních předpisů
http://linked.open...titaPredkladatele	Ústav fyzikální chemie J. Heyrovského AV ČR, v.v.i.
http://linked.open...dnocenehoVysledku	198025
http://linked.open...ai/riv/idVysledku	RIV/61388955:_____/11:00371365
http://linked.open...riv/jazykVysledku	eng - angličtina
http://linked.open.../riv/klicovaSlova	TITANIUM COMPOUNDS (ETA-5-C5ME5)2TIR; OLEFIN METATHESIS REACTION; TITANOCENE DICHLORIDES (en)
http://linked.open.../riv/klicoveSlovo	OLEFIN METATHESIS REACTION TITANIUM COMPOUNDS (ETA-5-C5ME5)2TIR TITANOCENE DICHLORIDES
http://linked.open...odStatuVydavatele	US - Spojené státy americké
http://linked.open...ontrolniKodProRIV	[A06CF4B9A231]
http://linked.open...i/riv/nazevZdroje	Organometallics
http://linked.open...in/vavai/riv/obor	CF
http://linked.open...ichTvurcuVysledku	4 (xsd:int)
http://linked.open...cetTvurcuVysledku	5 (xsd:int)
http://linked.open...vavai/riv/projekt	NQR spectroscopy of explosives and titanocene complexes Activation of small molecules by titanocene(II) and zirconocene(II) complexes. The structure and synthetic applications of transition metal complexes
http://linked.open...UplatneniVysledku	2011
http://linked.open...v/svazekPeriodika	30
http://linked.open...iv/tvurceVysledku	Mach, Karel Pinkas, Jiří Gyepes, R. Horáček, Michal Kubišta, Jiří
http://linked.open...ain/vavai/riv/wos	000290001900018
http://linked.open...n/vavai/riv/zamer	Struktura, reaktivita a dynamika molekulárních a biomolekulárních systémů: teorie, experiment, aplikace
issn	0276-7333
number of pages	6 (xsd:int)
http://bibframe.org/vocab/doi	10.1021/om2001487

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