About: Reduction-induced Double Bond Coordination and Multiple C-H Activation in Fully-substituted Titanocenes Bearing a Pendant Double Bond or an Eight-Membered Hydrocarbyl Ansa-Chain.

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About: Reduction-induced Double Bond Coordination and Multiple C-H Activation in Fully-substituted Titanocenes Bearing a Pendant Double Bond or an Eight-Membered Hydrocarbyl Ansa-Chain. Goto Sponge NotDistinct Permalink

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rdf:type	skos:Concept http://linked.opendata.cz/ontology/domain/vavai/Vysledek
Description	Reduction of isomeric, fully-substituted titanocene dichlorides having a pendant double bond, [TiCl2(.eta.5-C5Me4R)(.eta.5-C5Me5)] (R = CH2CH2CH=CH2, 1; R = CH(Me)CH=CH2, 2), with magnesium in THF in the presence of bis(trimethylsilyl)ethyne (btmse) affords different products depending on the alkenyl chain length. Whereas the reduction of 1 yields a compound with intramolecularly .eta.2-coordinated double bond, [Ti(.eta.5-C5Me5)(.eta.2:.eta.5-C5Me4(CH2CH2CH=CH2)] (3), compound 2 affords under identical conditions a product with two new Ti-C bonds, [Ti(.eta.1:.eta.1:.eta.5-C5Me3(CH2)(CH(Me)CH2CH2)}(.eta.5-C5Me5)] (4). The formation of 3 can be rationalized as a simple intramolecular stabilization of a titanocene intermediate formed by reductive removal of chloride ligands. The formation of 4 from the respective titanocene, however, requires formally an activation (oxidative addition) of one C-H bond at the methyl group adjacent to the unsaturated chain followed by a hydrogen shift. Reduction of isomeric, fully-substituted titanocene dichlorides having a pendant double bond, [TiCl2(.eta.5-C5Me4R)(.eta.5-C5Me5)] (R = CH2CH2CH=CH2, 1; R = CH(Me)CH=CH2, 2), with magnesium in THF in the presence of bis(trimethylsilyl)ethyne (btmse) affords different products depending on the alkenyl chain length. Whereas the reduction of 1 yields a compound with intramolecularly .eta.2-coordinated double bond, [Ti(.eta.5-C5Me5)(.eta.2:.eta.5-C5Me4(CH2CH2CH=CH2)] (3), compound 2 affords under identical conditions a product with two new Ti-C bonds, [Ti(.eta.1:.eta.1:.eta.5-C5Me3(CH2)(CH(Me)CH2CH2)}(.eta.5-C5Me5)] (4). The formation of 3 can be rationalized as a simple intramolecular stabilization of a titanocene intermediate formed by reductive removal of chloride ligands. The formation of 4 from the respective titanocene, however, requires formally an activation (oxidative addition) of one C-H bond at the methyl group adjacent to the unsaturated chain followed by a hydrogen shift. (en)
Title	Reduction-induced Double Bond Coordination and Multiple C-H Activation in Fully-substituted Titanocenes Bearing a Pendant Double Bond or an Eight-Membered Hydrocarbyl Ansa-Chain. Reduction-induced Double Bond Coordination and Multiple C-H Activation in Fully-substituted Titanocenes Bearing a Pendant Double Bond or an Eight-Membered Hydrocarbyl Ansa-Chain. (en)
skos:prefLabel	Reduction-induced Double Bond Coordination and Multiple C-H Activation in Fully-substituted Titanocenes Bearing a Pendant Double Bond or an Eight-Membered Hydrocarbyl Ansa-Chain. Reduction-induced Double Bond Coordination and Multiple C-H Activation in Fully-substituted Titanocenes Bearing a Pendant Double Bond or an Eight-Membered Hydrocarbyl Ansa-Chain. (en)
skos:notation	RIV/61388955:_____/03:54030014!RIV/2004/AV0/A54004/N
http://linked.open.../vavai/riv/strany	154;166
http://linked.open...avai/riv/aktivita	P Z
http://linked.open...avai/riv/aktivity	P(GA203/02/0436), P(IAA4040004), Z(AV0Z4040901)
http://linked.open...iv/cisloPeriodika	1/2
http://linked.open...vai/riv/dodaniDat	2004
http://linked.open...aciTvurceVysledku	Petrusová, Lidmila Horáček, Michal Mach, Karel Kubišta, 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	624900
http://linked.open...ai/riv/idVysledku	RIV/61388955:_____/03:54030014
http://linked.open...riv/jazykVysledku	eng - angličtina
http://linked.open.../riv/klicovaSlova	titanocene; titanuim; X-ray crystallography (en)
http://linked.open.../riv/klicoveSlovo	X-ray crystallography titanocene titanuim
http://linked.open...odStatuVydavatele	CH - Švýcarská konfederace
http://linked.open...ontrolniKodProRIV	[A70A99E507BC]
http://linked.open...i/riv/nazevZdroje	Journal of Organometallic Chemistry
http://linked.open...in/vavai/riv/obor	CF
http://linked.open...ichTvurcuVysledku	4 (xsd:int)
http://linked.open...cetTvurcuVysledku	6 (xsd:int)
http://linked.open...ocetUcastnikuAkce	0 (xsd:int)
http://linked.open...nichUcastnikuAkce	0 (xsd:int)
http://linked.open...vavai/riv/projekt	Application of Crystallographic Databases in Scientific Practice Reactivity of pendant double bonds in the coordination sphere of titanium
http://linked.open...UplatneniVysledku	2003
http://linked.open...v/svazekPeriodika	667
http://linked.open...iv/tvurceVysledku	Císařová, I. Mach, Karel Štěpnička, P. Horáček, Michal Kubišta, Jiří Petrusová, Lidmila
http://linked.open...n/vavai/riv/zamer	Objasňování zákonitostí vztahů struktury a vlastností - zejména dynamiky a chemické reaktivity - látek a molekulárních systémů
issn	0022-328X
number of pages	13 (xsd:int)

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