Formation of fulvene and dimethylenecyclopentenyl titanium complexes from bis(η5-tetramethylcyclopentadienyl)titanium(IV) precursors

A mixture of isomeric (Me4C5H)(Me3C5(CH2)H)TiMe compounds was obtained by thermally induced methane elimination from (Me4C5H)2TiMe2 at 130°C, analogous to the formation of (Me5C5)(Me4C5(CH2))TiMe. The compound (Me5C5)(Me3C5(CH2)2Ti was newly prepared in 27% yield by boiling a (Me5C5)2TiCl2LiAlH4 mixture in toluene, followed by sublimation of the soluble product. By an analogous process, (Me4C5H)(Me2C5(CH2)2H)Ti was obtained in 10% yield. Neither type of complex was formed by either method from titanocene derivates with fewer methyl groups at cyclopentadienyl ligands.