Zirconium and hafnium complexes of the thio(bisphenolato) ligand: synthesis, structural characterization and testing as 1-hexenepolymerizationcatalysts

Thio(bisphenolato) complexes of the type [M2(mu-tbop-kappa3O,S,O)2Cl4] [M = Zr 1, Hf 2 and tbop = 2,2-thiobis{4-(1,1,3,3-tetramethyl-butyl)phenolate}] were prepared by HCl elimination from tbopH2 and MCl4. Substitution of the chlorides in 1 and 2 by 2,6-diisopropylphenolato groups (dipp) generates new compounds [M2(mu-tbop-kappa3O,S,O)2(dipp)4] (M = Zr 3, Hf 4). The structures of 1-4 were confirmed by NMR spectroscopy; complexes 3 and 4 were further investigated by X-ray crystallography. These studies showed 1-4 to be dimers either in the solid state or in solution and to have metal centers adopting distorted octahedral geometry. However treatment of MCl4 with [Al2(mu-OEt)2(tbop-kappa3O,S,O…