Mixed-ligand iminopyrrolato-salicylaldiminato group 4 metal complexes: Optimising catalyst structure for ethylene/propylene copolymerisations

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• 作者：Lewis M. Broomfield ; Yann Sarazin ; Joseph A. Wright ; David L. Hughes ; William Clegg ; Ross W. Harrington ; Manfred Bochmann
• 关键词：Titanium ; Zirconium ; Ethene ; Copolymerization ; Salicylaldiminate ; Iminopyrrolate
• 刊名：Journal of Organometallic Chemistry
• 出版年：2007
• 期刊代码：64_0022328x
• 类别：ch
• 出版时间：1 October 2007
• 卷：692
• 期：21
• 页码：4603-4611
• 文件大小：427 K

摘要

Treatment of MCl₃(OC₆H₃-2-^tBu-6-CHmg src="http://www.sciencedirect.com/scidirimg/entities/dbnd" alt="double bond; length as m-dash" border=0>NC₆F₅)(THF) (M = Ti, Zr) with a variety of different potassium iminopyrrolate salts (K⁺[RNmg src="http://www.sciencedirect.com/scidirimg/entities/dbnd" alt="double bond; length as m-dash" border=0>CHC₄H₃N]⁻), (R = phenyl, cyclo-hexyl, ethyl) afforded the corresponding titanium and zirconium mixed-ligand complexes MCl₂(N–O)(N–N). The molecular structures of TiCl₂(OC₆H₃-2-^tBu-6-CHmg src="http://www.sciencedirect.com/scidirimg/entities/dbnd" alt="double bond; length as m-dash" border=0>NC₆F₅)(C₂H₅Nmg src="http://www.sciencedirect.com/scidirimg/entities/dbnd" alt="double bond; length as m-dash" border=0>CHC₄H₃N) (1c), TiCl₂(OC₆H₃-2-^tBu-6-CHmg src="http://www.sciencedirect.com/scidirimg/entities/dbnd" alt="double bond; length as m-dash" border=0>NC₆F₅)(C₆H₁₁Nmg src="http://www.sciencedirect.com/scidirimg/entities/dbnd" alt="double bond; length as m-dash" border=0>CHC₄H₃N) (1b) and ZrCl₂(OC₆H₃-2-^tBu-6-CHmg src="http://www.sciencedirect.com/scidirimg/entities/dbnd" alt="double bond; length as m-dash" border=0>NC₆F₅)(C₆H₁₁Nmg src="http://www.sciencedirect.com/scidirimg/entities/dbnd" alt="double bond; length as m-dash" border=0>CHC₄H₃N) (2b) show distorted octahedral geometries with trans-O⁻,N⁻/cis-Cl₂ arrangements. On activation with MAO the titanium (iminopyrrolato)(salicylaldiminato) complexes show excellent activities in ethylene polymerisation and are significantly more effective ethylene/propylene copolymerisation catalysts, both in terms of activity and propene incorporation, than either of the parent complexes. The ethylene–propylene copolymers show ca. 80%1,2 regioselectivity and at high propylene incorporation tend towards an alternating structure.