Synthesis of Titanium(IV) and Zirconium(IV) Complexes with an [OSSO]-Type Bis(phenolate) Ligand Bearing a trans-Cyclohexane-1,2-diyl Ring and 1-Hexene Polymerization

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• 作者：Akihiko Ishii ; Kanako Asajima ; Tomoyuki Toda ; Norio Nakata
• 刊名：Organometallics
• 出版年：2011
• 出版时间：June 13, 2011
• 年：2011
• 卷：30
• 期：11
• 页码：2947-2956
• 全文大小：1085K
• 年卷期：v.30,no.11(June 13, 2011)
• ISSN：1520-6041

文摘

The Ti(IV) and Zr(IV) complexes 9 and 11 with a new [OSSO]-type bis(phenolate) ligand bearing a trans-cyclohexane-1,2-diyl ring (6) were synthesized. The reaction of 6 with Ti(OiPr)₄ in toluene gave the two C₂-symmetric, diastereomeric Ti complexes (螞*,S*,S*)-9 and (螖*,S*,S*)-9, the latter of which was characterized by X-ray crystallography. The reaction of 6 with Zr(CH₂Ph)₄ also provided a mixture of the two C₂-symmetric diastereomers (螞*,S*,S*)-11 and (螖*,S*,S*)-11. Polymerization of 1-hexene employing 11 as the precatalyst yielded isotactic poly(1-hexene) with high activity. In relation to the activity, an NMR study was carried out for the cationic zirconium complex 12⁺[B(CH₂Ph)(C₆F₅)₃]^{鈭?/sup> in comparison with the corresponding complex 13+[B(CH₂Ph)(C₆F₅)₃]鈭?/sup>, bearing a trans-cyclooctane-1,2-diyl ring in the ligand.}