SYNTHESIS AND THERMOLYSIS OF CP-ASTERISK(C5ME4CH2)TIR COMPLEXES

Substitution of the chloride in CpFvTiCl with MR (Fv = C5Me4CH2; R = Me, CH2SiMe3, CH2CMe3, CH = CH2, M = Li; R = CH2Ph, M = K; R = C3H5, M = MgCl; R = Ph, M = Na . NaCl) gives CpFvTiR. NMR spectroscopic evid ence points towards a series of structurally related compounds with a bent-sandwich geometry. The substituent R is positioned in the wedge, midway below the exocyclic methylene group and a neighbouring methyl g roup of the fulvene. Thermolysis of CpFvTiR gives, dependent on the s ubstituent R, reduction to CpFvTi (R = CH2Ph) or the double ring meta llated Cp[C5Me3(CH2)(2)]Ti (R = CH2XMe3, X = C, Si) or Cp*FvTiCH=CHMe (R = eta(3)-C3H5).