Novel zirconium-iron multinuclear complex catalysts for olefin polymerizations

Makoto Mitani, Michiya Hayakawa, Tohru Yamada, Teruaki Mukaiyama

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Abstract

Novel zirconium-iron dinuclear complexes, [FcSiMe2(R1R2Cp)ZrCl2Cp] (Fc; Ferrocenyl, R1 =R2 =H; 2a, R1 =Me, R2 =H; 2b, R1 =R2 =Me; 2c, R1 =Ph, R2 =H; 2d), [FcSiMe2Cp{ZrCl2(Me5Cp)}] (3a), hafnium-iron dinuclear complex, [FcSiMe2Cp{HfCl2(Me5Cp)}] (3b) and zirconium-iron trinuclear complex, [ZrCl2(FcSiMe2Cp)2] (4), were synthesized and complexes 2d and 4 were characterized by an X-ray diffraction method. Olefin polymerizations were conducted by using these multimetallic zirconocene catalysts with the coexistence of methylaluminoxane or tetrakis(pentafluorophenyl)borates. The maximum catalytic activities of complexes 2, 3 and 4 were observed at low temperatures (15-45 °C) in ethylene polymerization, contrary to the conventional zirconocene catalyst ([ZrCl2Cp2]), showing the maximum activity at between 70-80 °C. A detailed investigation of ethylene polymerization and NMR measurements of the active species suggested that the interesting behavior of these complexes arose from an electronic cooperative effect between the zirconium and iron atoms. It was also revealed that complexes 2 were highly reactive toward propylene or diene in the copolymerization of ethylene and propylene or terpolymerization of ethylene, propylene and diene.

Original languageEnglish
Pages (from-to)2967-2976
Number of pages10
JournalBulletin of the Chemical Society of Japan
Volume69
Issue number10
DOIs
Publication statusPublished - 1996 Oct

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ASJC Scopus subject areas

  • Chemistry(all)

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