Synthetic and reactivity studies of mono- and dicyclopentadienyl titanium, zirconium and hafnium complexes with the chlorodimethylsilyl-cyclopentadienyl ligand. X-ray molecular structure of Hf{(η5-C5H4)SiMe2OSiMe2(η5-C5H4)}Cl2 and Zr(η5-1,3-tBu2C5H3)(η5-C

Reaction of the disilylated cyclopentadiene C5H4(SiClMe2)(SiMe3) with HfCl4, in heptane, gave the monocyclopentadienyl complex Hf(η5-C5H4SiClMe2)Cl3 (1c). Addition of two equivalents of C5H5(SiClMe2) to a solution of MCl4, in toluene under reflux and in the presence of two equivalents of NEt3, afforded the dichloro derivatives M(η5-C5H4SiClMe2)2Cl2 [M=Ti (2a), Hf (2c)]. Compounds 2a and 2c react with a stoichiometric amount of water with selective hydrolysis of the SiCl bonds to give the tetramethyldisiloxane-bridged diciclopentadienyl complexes M{(η5-C5H4)SiMe2OSiMe2(η5-C5H4)}Cl2 [M=Ti (3a), Hf (3c)]. The reaction of the trichloro metal compounds M(η5-C5H4SiClMe2)Cl3 with Tl(1,3-tBu2C5H3), K(C5Me5) or Tl(C5H5) afforded the dichloro mixed dicyclopentadienyl MCp′(η5-C5H4SiClMe2)Cl2 derivatives [Cp′=1,3-tBu2C5H3, M=Ti (4a), Zr (4b), Hf (4c); Cp′=C5Me5, M=Zr (5b), Hf (5c); Cp′=C5H5, M=Hf (6c)]. The SiCl bond of the mixed dicyclopentadienyl complexes M(η5-1,3-tBu2C5H3)(η5-C5H4SiClMe2)Cl2, [M=Ti (4a), Zr (4b), Hf (4c)] reacts selectively with one equivalent of LiNHtBu in toluene at 50–60°C to give the amidosilyl(cyclopentadienyl) compounds M(η5-1,3-tBu2C5H3)(η5-C5H4SiMe2NHtBu)Cl2, [M=Ti (7a), Zr (7b), Hf (7c)]. The same reaction with two equivalents of the lithium amide gives the ansa-cyclopentadienylsilyl-amido compounds M(η5-1,3-tBu2C5H3)(η5-C5H4SiMe2-η-NtBu)Cl [M=Ti (8a), Zr (8b), Hf (8c)]. The X-ray molecular structure of Hf{(η5-C5H4)SiMe2OSiMe2(η5-C5H4)}Cl2 (3c) and Zr(η5-1,3-tBu2C5H3)(η5-C5H4SiMe2-η-NtBu)Cl (8b) have been determined by diffraction methods.