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Reduction-Induced Exclusive Activation of the ansa-1,2-Bis(dimethylsilylene)ethane Chain in ansa-Permethyltitanocene Compounds

SYSNO ASEP	0351877
Document Type	J - Journal Article
R&D Document Type	Journal Article
Subsidiary J	Článek ve WOS
Title	Reduction-Induced Exclusive Activation of the ansa-1,2-Bis(dimethylsilylene)ethane Chain in ansa-Permethyltitanocene Compounds
Author(s)	Pinkas, Jiří (UFCH-W)_{RID, ORCID} Lukešová, Lenka (UFCH-W) Gyepes, R. (CZ) Císařová, I. (CZ) Kubišta, Jiří (UFCH-W)_{RID, ORCID} Horáček, Michal (UFCH-W)_{RID, ORCID} Mach, Karel (UFCH-W)_{ORCID, RID}
Source Title	Organometallics. - : American Chemical Society - ISSN 0276-7333 Roč. 29, č. 21 (2010), s. 5199-5208
Number of pages	10 s.
Language	eng - English
Country	US - United States
Keywords	ansa-1,2-bis(dimethylsilylene)ethane ; ansa-permethyltitanocene ; titanium
Subject RIV	CF - Physical ; Theoretical Chemistry
R&D Projects	IAA400400708 GA AV ČR - Academy of Sciences of the Czech Republic (AV ČR)
	LC06070 GA MŠMT - Ministry of Education, Youth and Sports (MEYS)
CEZ	AV0Z40400503 - UFCH-W (2005-2011)
UT WOS	000283572100065
DOI	10.1021/om1003623
Annotation	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.
Workplace	J. Heyrovsky Institute of Physical Chemistry
Contact	Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196
Year of Publishing	2011

Number of the records: 1