The syntheses and characterisation of C9H6(X)(CH2)(3)N(SiMe3)2 (X = H (2), SiMe3 (4), Li (3)) are described. The reactions of 4 with TiCl4, [TiCp*Cl-3] and NbCl5 led to the isolation of [Ti{N(H)(CH2)(3)C9H6SiMe3}Cl-3] (5), [TiCp*{N(H)(CH2)(3)(C9H6SiMe3)}Cl-2] (8) and [Nb{N(CH2)(3)(C9H6SiMe3)}Cl-3](2)(THF)-T-. (9), respectively. The reaction of 3 with TiCl4 led to the ansa-bridged indenyl-amido complex [Ti{eta(5):sigma,pi(C9H6)(CH2)(3)N(SiMe3)}Cl-2] (7) and with [Mo(CO)(2)(CH3CH2CN)(2)(C3H5)Cl] gave [{eta(5)-C9H6(CH2)(3)N(SiMe3)(2)}Mo(CO)(2)(C3H5)] (10). Two conformers, corresponding to the limit orientations of the allyl ligand (endo and exo) have been identified in solution, by NMR. The activation parameters for the slow endo/exo isomerisation process were determined. (C) 2003 Elsevier B.V. All rights reserved.