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Irregular Cyclization Reactions in Titanocenes Bearing Pendant Double Bonds
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SYSNO ASEP 0101060 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Ostatní články Title Irregular Cyclization Reactions in Titanocenes Bearing Pendant Double Bonds Title Nepravidelné cyklizační reakce titanocenů nesoucích visící dvojnou vazbu Author(s) Lukešová, Lenka (UFCH-W)
Horáček, Michal (UFCH-W) RID, ORCID
Štěpnička, P. (CZ)
Gyepes, R. (CZ)
Císařová, I. (CZ)
Kubišta, Jiří (UFCH-W) RID, ORCID
Mach, Karel (UFCH-W) ORCID, RIDSource Title Journal of Organometallic Chemistry. - : Elsevier - ISSN 0022-328X
Roč. 689, č. 11 (2004), s. 1919-1929Number of pages 11 s. Language eng - English Country CH - Switzerland Keywords titanium ; magnesium ; titanocene Subject RIV CF - Physical ; Theoretical Chemistry R&D Projects GA203/02/0774 GA ČR - Czech Science Foundation (CSF) GA203/99/M037 GA ČR - Czech Science Foundation (CSF) GA203/02/0436 GA ČR - Czech Science Foundation (CSF) CEZ AV0Z4040901 - UFCH-W Annotation Reduction of methyl-substituted titanocene dichlorides bearing pendant double bonds [TiCl2{.eta.5-C5Me4(CH2CMe=CH2)}2] (1) and [TiCl2{.eta.5-C5Me4(SiMe2(CH2)2CH=CH2)}2] (2) with magnesium yielded diamagnetic Ti(IV) compound [Ti{(.eta.1:.eta.1:.eta.5-C5Me3(CH2)(CH2CH(Me)CH2)}{.eta.5-C5Me4(CH2C(Me)=CH2)}] (4) and paramagnetic Ti(III) compound [Ti{.eta.5-C5Me4(SiMe2CH2CH=CHMe)}(.mu.-.eta.3,.eta.1:.eta.5,.eta.1(Ti:Mg){C5Me3(CH2)(SiMe2CHCHCMe)})Mg(OC4H8)2] (6), respectively. The reluctance of titanocene intermediates to undergo intramolecular cyclization to cyclopentadienyl-ring-tethered titanacycles (as typically observed) can be explained by a shortness of 2-methylallyl group and steric hindrance of its double bond in the former case and, in the latter case, by an attack of magnesium on the titanocene intermediate, faster than cyclization reaction. Workplace J. Heyrovsky Institute of Physical Chemistry Contact Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196 Year of Publishing 2005
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