Abstract
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(η5-CH2Me2SiC5Me4)2] (8) with magnesium. The compound [Ti(η2:η5:η5-C5Me4SiMe2CH═CHSiMe2C5Me4)] (10), with the double bond back-bonded to titanium(II), is formed by thermolysis of ansa-[TiMe2(η5-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 π-coordinated to an ansa-titanocene moiety. The paramagnetic compound ansa-[TiIII{η1:η5:η5-C5Me4SiMe2CHCH2SiMe2C5Me4}] (12), with the ansa-chain tethered to titanium, arises from demethanation of transiently formed ansa-[TiIIIMe(η5-CH2Me2SiC5Me4)2] or by the reduction of 8 with magnesium in tetrahydrofuran. The intermediacy of magnesium as a hydrogen transfer agent in the mechanism of the latter reaction is suggested.
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