Synthesis and thermolysis of Cp(C5Me4CH2)TiR complexes

Article abstract of DOI:10.1016/S0022-328X(96)06746-0

Substitution of the chloride in Cp*FvTiCl 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 Cp*FvTiR. NMR spectroscopic evidence 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 group of the fulvene. Thermolysis of Cp*FvTiR gives, dependent on the substituent R, reduction to Cp*FvTi (R = CH₂Ph) or the double ring metallated Cp*[C₅Me₃(CH₂)₂]Ti (R = CH₂XMe₃, X = C, Si) or Cp*FvTiCH=CHMe (R = η³-C₃H₅).