Thermolysis of titanocene methyl compounds bearing t-butyl- and benzyltetramethylcyclopentadienyl ligands |
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Authors: | Ji?í Pinkas Ana Conde Michal Horá?ek Karel Mach |
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Institution: | a J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolejškova 3, 182 23 Prague 8, Czech Republic b Department of Inorganic Chemistry, Faculty of Science, Charles University, Hlavova 2030, 128 40 Prague 2, Czech Republic c Departamento de Química Inorgánica, Orgánica y Bioquímica, Facultad de Ciencias del Medio Ambiente, Universidad de Castilla-La Mancha, Avd. Carlos III, s/n, 45071 Toledo, Spain |
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Abstract: | 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. |
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Keywords: | Titanium t-Butyltetramethylcyclopentadienyl Benzyltetramethylcyclopentadienyl Thermolysis Titanocene methyl Titanocene dimethyl |
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