Synthesis and characterization of titanium and zirconium complexes with silicone-bridged phenoxycyclopentadienyl ligands |
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Authors: | Hidenori Hanaoka Hiroshi Souda Yoshiaki Oda Akio Imai |
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Affiliation: | a Organic Synthesis Research Laboratory, Sumitomo Chemical Co., Ltd., 1-98, Kasugadenaka 3-chome, Konohana-ku, Osaka 554-8558, Japan b Genomic Science Laboratories, Dainippon Sumitomo Pharma Co., Ltd., 1-98, Kasugadenaka 3-chome, Konohana-ku, Osaka 554-0022, Japan c Petrochemicals Research Laboratory, Sumitomo Chemical Co., Ltd., Kitasode, Sodegaura, Chiba 299-0295, Japan |
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Abstract: | Dimethylsilyl(2,3,4,5-tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride (1a), a useful catalyst precursor for olefin copolymerization, was synthesized at high yield starting from allyl-protected phenolic ligand 3a,which was first treated with 2 equiv. of n-BuLi to selectively give the dilithium salt of 3a along with 1-heptene, a coupling product of a protected allyl ether moiety and butyl anion. Addition of TiCl4 to the resulting dilithium salt of 3a in toluene afforded 1a in 50% isolated yield. This methodology could be applied to the preparation of related titanium and zirconoium complexes 1b-1d, 8 with silicone-bridged Cp-phenoxy ligands, whereas the reaction starting from methyl-protected precursor 2a did not produce the zirconium complex 8. Copolymerization of ethylene and 1-hexene with the newly prepared complexes was also investigated. |
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Keywords: | Titanium Silicone-bridged Phenoxycyclopentadienyl ligand Deallylation |
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