Thermolysis of titanocene methyl compounds bearing t-butyl- and benzyltetramethylcyclopentadienyl ligands

Elimination of methane during thermolysis of title compounds results in the formation of σ-Ti–C bond to t-butyl or benzyl group. The t-butyl-containing titanocene methyl compound [Ti(III)Me(η5-C5Me4t-Bu)2] (5) eliminates methane at 110 °C to give cleanly [Ti(III)(η5:η1-C5Me4CMe2CH2)(η5-C5Me4t-Bu)] (6). The methyl derivative of analogous benzyl-containing titanocene [Ti(III)Me(η5-C5Me4CH2Ph)2] was not isolated because it eliminated methane at ambient temperature to give [Ti(III)(η5:η1-C5Me4CH2-o-C6H4)(η5-C5Me4CH2Ph)] (7) with one phenyl ring linked to titanium atom in ortho-position. The corresponding titanocene dimethyl compound [TiMe2{η5-C5Me4t-Bu)}2] (9) eliminates two methane molecules at 110 °C to give the singly tucked-in 1,1-dimethylethane-1,2-diyl-tethered titanocene [Ti{η5:η1:η1-C5Me3(CH2)(CMe2CH2)}(η5-C5Me4t-Bu)] (11). In distinction, the analogous benzyl derivative [TiMe2(η5-C5Me4CH2Ph)2] (10) eliminates at 110 °C only one methane molecule to afford [TiMe(η5:η1-C5Me4CH2-o-C6H4)(η5-C5Me4CH2Ph)] (12) containing one phenyl group attached to titanium in o-position and one methyl group persisting on the titanium atom. This compound is stable at 150 °C for at least 3 h. The crystal structures of 5, 6, 7, and 10 were determined.