Citation: Zhang Lei, Ma Haiyan. Ethylene-Bridged Multi-Substituted Indenyl-Fluorenyl Zirconocene and Hafnocene Complexes: Synthesis, Structure and Catalytic Behavior for Propylene Selective Oligomerization[J]. Acta Chimica Sinica, ;2020, 78(8): 778-787. doi: 10.6023/A20030092 shu

Ethylene-Bridged Multi-Substituted Indenyl-Fluorenyl Zirconocene and Hafnocene Complexes: Synthesis, Structure and Catalytic Behavior for Propylene Selective Oligomerization

Zhang Lei ,
Ma Haiyan ^,

Laboratory of Organometallic Chemistry, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237

Corresponding author: Ma Haiyan, haiyanma@ecust.edu.cn
Received Date: 27 March 2020
Available Online: 16 June 2020
Fund Project: the National Natural Science Foundation of China 21274041Project supported by the National Natural Science Foundation of China (No. 21274041)

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In metallocene-mediated propylene polymerization, β-methyl elimination (β-Me elimination) is considered as the key chain-release step for obtaining allyl-terminated products, which are highly preferred as macro(co)monomers or building blocks for preparing novel polymers. However, for most metallocene catalysts the transfer of a β-methyl is instinctively less favored due to its steric and electronic disadvantages. Up to date, very few cases have been found to be efficient for triggering selective β-methyl elimination. In this work, a series of novel ansa-metallocene complexes, ansa-C₂H₄-{2-Me-3-Bn- 5, 6-[1, 3-(CH₂)₃]Ind}(Flu)ZrCl₂ (C1), ansa-C₂H₄-{2-Me-3-Bn-5, 6-[1, 3-(CH₂)₃]Ind}(2, 7-^tBu₂-Flu)ZrCl₂ (C2), ansa-C₂H₄-{2-Me-3-Bn-5, 6-[1, 3-(CH₂)₃]Ind}(3, 6-^tBu₂-Flu)ZrCl₂ (C3) and ansa-C₂H₄-{2-Me-3-Bn-5, 6-[1, 3-(CH₂)₃]Ind}(Flu)HfCl₂ (C4), were synthesized via the reaction of the dilithium salts of the corresponding proligand with 1 equiv. of ZrCl₄ or HfCl₄ in Et₂O. All complexes were characterized by ¹H NMR, ¹³C NMR and elemental analysis. The molecular structures of complexes C1, C2, and C3 were further determined via X-ray diffraction method. In the solid state, these complexes adopted an indenyl-backward orientation with rotation angles (RA: the orientation of the indenyl ring with respect to the fluorenyl ring) ranging from －11.30° to －17.07°. Upon activation with modified methylaluminoxane (MMAO) or AlⁱBu₃/ [Ph₃C][B(C₆F₅)₄] (TIBA/TrB), all these complexes exhibited moderate to high activities for propylene oligomerization at 40~100 ℃, affording propylene oligomers with both allyl and vinylidene chain-ends, which arised from β-Me elimination and β-H eliminations respectively. The methyl group at the 2-position of the indenyl ring turned out to have negative effects on both catalytic activity and β-Me elimination selectivity. Zirconocene complex C1 polymerized propylene to give oligomers with 40%~52% allyl chain-ends. However, further modification of the fluorenyl moiety allowed a great improvement in β-Me elimination selectivity. At 40~100 ℃, zirconocene complexes C2 and C3 bearing a 2, 7- or 3, 6-di-tert-butyl- substituted fluorenyl moiety showed significantly higher β-Me elimination selectivities (C2, 81%~86%; C3, 68%~77%), affording propylene oligomers (M_n 400~4500 g·mol^－1) with allyl-dominant chain-ends. Moreover the substitution pattern of the fluorenyl moiety also substantially influenced the catalytic activities. The incorporation of an electron-donating 2, 7-di-tert-butyl groups on the fluorenyl moiety led to notably increased catalytic activities of complex C2 at higher temper-atures above 60 ℃, while complex C3 bearing a 3, 6-di-tert-butyl-substituted fluorenyl moiety showed lowest activities among the zirconocene series due to its overcrowded coordination sites. Compared with its zirconocene analogue, the hafnocene complex C4 activated with TIBA/TrB proved to be even more selective toward β-Me elimination, and meanwhile gave products with much lower molecular weights. At 100 ℃, the hafnocene system mainly oligomerized propylene to dimers and trimers. Studies on the dependence of the product molecular weight and the chain-release selectivity on monomer concentration suggested that both β-Me and β-H elimination involved in these systems mainly operate in a bimolecular pathway.
- metallocene catalyst,
- propylene oligomerization,
- allyl chain-end,
- β-methyl elimination
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