Silyl and siloxanediyl cyclopentadienyl titanium and zirconium complexes: Synthesis and reactivity. X-ray molecular structure of Zr{η5-C5H4SiMe 2(μ-OH)}(μ-Cl)Cl2l2

Article abstract of DOI:10.1016/S0277-5387(97)00491-9

Chloro(dimethyl)silyl-η⁵-cyclopentadienyl group 4 metal complexes of the type [M(η⁵-C₅H₄SiMe₂ Cl)Cl₃] (M = Ti 1, Zr 2) react with thallium salts Tl(C₅H₄R) (R = H, SiMe₃) to give mixed dicyclopentadienyl derivatives [M(η⁵-C₅H₄R)(η⁵-C ₅H₄SiMe₂Cl)Cl₂], (M = Ti, R = H 3, R = SiMe₃ 4; M = Zr, R = H 5, R = SiMe₃ 6) in high yield. Hydrolysis of complexes 3 and 4 affords the dinuclear complexes [Ti (η⁵-C₅H₄R)Cl₂] ₂{μ-[(η⁵-C₅H₄SiMe ₂)₂O]} (R = H 7, R = SiMe₃ 8) containing a siloxanyl bridge, by elimination of two equivalents of HCl. Reactions of complexes 1 with hydroxo containing reagents such as anhydrous LiOH and SiPh₂(OH)₂ give the derivatives [Ti(η⁵C₅H₄SiMe₂Cl)Cl ₂]₂(μ-O)], 9 and Ti[η⁵-C₅H₄SiMe₂OSiPh ₂-η¹-O)]Cl₂, 10 identified by analytical, spectrometric and spectroscopic data. Treatment of analogous complex 2 with water produces the dimeric monocyclopentadienyl zirconium trichloride adduct [Zr(η⁵-C₅H₄ SiMe₂OH)Cl₃]₂, 11. Compound 11 has been characterized by X-ray crystallography.