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Zirconium and hafnium complexes of the thio(bisphenolato) ligand: synthesis structural characterization and testing as 1-hexene polymerization catalysts.
Autorzy
Rok wydania
2009
Czasopismo
Strony
8846-8853
DOI
10.1039/B907560G
Kolekcja
Język
Angielski
Typ publikacji
Artykuł
Thio(bisphenolato) complexes of the type [M2(µ-tbop-κ3O,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(µ-tbop-κ3O,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(µ-OEt)2(tbop-κ3O,S,O)2] or [Al2(µ-tbop-κ3O,S,O)2Me2] gave heterotrinuclear complexes [M(tbop-κ3O,S,O)2Cl2(µ-AlX2)2] (M = Zr, X = Cl 5, X = Me 7 and M = Hf, X = Cl 6, X = Me 8) for which the single-crystal X-ray diffraction analysis showed zirconium and hafnium centers to have eight-coordinate dodecahedral geometry. Complexes 1–6 after activation with aluminium alkyls and supporting on MgCl2 showed a lack of activity in the ethene polymerization process and moderate activity towards 1-hexene producing high molecular weight atactic poly(1-hexenes).
Adres publiczny
https://doi.org/10.1039/B907560G