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Reduction-Induced Exclusive Activation of the ansa-1,2-Bis(dimethylsilylene)ethane Chain in ansa-Permethyltitanocene Compounds
- 1.0351877 - ÚFCH JH 2011 RIV US eng J - Journal Article
Pinkas, Jiří - Lukešová, Lenka - Gyepes, R. - Císařová, I. - Kubišta, Jiří - Horáček, Michal - Mach, Karel
Reduction-Induced Exclusive Activation of the ansa-1,2-Bis(dimethylsilylene)ethane Chain in ansa-Permethyltitanocene Compounds.
Organometallics. Roč. 29, č. 21 (2010), s. 5199-5208. ISSN 0276-7333. E-ISSN 1520-6041
R&D Projects: GA AV ČR IAA400400708; GA MŠMT(CZ) LC06070
Institutional research plan: CEZ:AV0Z40400503
Keywords : ansa-1,2-bis(dimethylsilylene)ethane * ansa-permethyltitanocene * titanium
Subject RIV: CF - Physical ; Theoretical Chemistry
Impact factor: 3.888, year: 2010
The ansa-1,2-bis(dimethylsilylene)ethane chain is exclusively activated when the parent ansa-permethyltitanocene compounds are reduced to titanium(II) either by thermolysis of titanium-methyl bonds or by the reduction of the parent titanocene dichloride ansa-[TiCl2(eta(5)-CH2Me2-SiC5Me4)(2)] (8) with magnesium. The compound [Ti(eta(2):eta(5):eta(5)-C5Me4SiMe2CH=CHSiMe2C5Me4)] (10), with the double bond back-bonded to titanium(II), is formed by thermolysis of ansa-[TiMe2(eta(5)-CH2Me2SiC5Me4)(2)] (9) with elimination of methane or by hydrogen transfer from the ansa-chain to easily leaving ethene or 1,4-bis(trimethylsilyl)buta-1,3-diyne pi-coordinated to an ansa-titanocene moiety. The paramagnetic compound ansa-[Ti-III{eta(1):eta(5):eta(5)-C5Me4SiMe2CHCH2SiMe2C5Me4}] (12), with the anso-chain tethered to titanium, arises from demethanation of transiently formed ansa-[(TiMe)-Me-III(eta(5)-CH2Me2SiC5Me4)(2)] or by the reduction of 8 with magnesium in tetrahydrofuran.
Permanent Link: http://hdl.handle.net/11104/0191523
Number of the records: 1