Citation: Lei Zhang, Bin Zhang, Haiyan Ma. Ethylene-bridged Indenyl-fluorenyl Metallocene Complexes for Efficient Preparation of Allyl-terminated Propylene Oligomers and Polymers via Selective β-Methyl Transfer[J]. Chinese Journal of Polymer Science, ;2019, 37(6): 578-590. doi: 10.1007/s10118-019-2224-1 shu

Ethylene-bridged Indenyl-fluorenyl Metallocene Complexes for Efficient Preparation of Allyl-terminated Propylene Oligomers and Polymers via Selective β-Methyl Transfer

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

Corresponding author: Haiyan Ma, haiyanma@ecust.edu.cn
Received Date: 7 December 2018
Revised Date: 10 January 2019
Available Online: 1 March 2019

Four C₁-symmetric ansa-metallocene complexes, C₂H₄(Ind)(2,7-^tBu₂-Flu)ZrCl₂ (4), C₂H₄(3-Bn-Ind)(2,7-^tBu₂-Flu)ZrCl₂ (5), C₂H₄(3-Bn-Ind)(3,6-^tBu₂-Flu)ZrCl₂ (6), and C₂H₄(3-Bn-Ind)(2,7-^tBu₂-Flu)HfCl₂ (7), were synthesized and characterized. The structures of complexes 4, 5, and 7 were further determined via X-ray diffraction studies. Upon activation with modified methylaluminoxane (MMAO) or AlⁱBu₃/[Ph₃C][B(C₆F₅)₄] (TIBA/TrB), most of these complexes showed high efficiency in catalyzing propylene oligomerization/polymerization to afford products dominantly with allyl terminals via selective β-methyl transfer (β-Me transfer). The introduction of 3-benzyl group on the indenyl ring of the complexes was found to be crucial in enabling highly selective β-Me transfer during the polymerization process, leading to selectivities up to 89% obtained by zirconocene complexes 5 and 6, and up to 91% obtained by hafnocene complex 7. Detailed chain-end analysis by ¹H-NMR, ¹³C-NMR, and MALDI-TOF mass spectroscopy revealed that the allyl chain-ends of the polymeric products resulted from a selective β-Me transfer process after two successively primary insertions of the monomer. Further studies concerning the dependence of chain release selectivity as well as the molecular weight of products on monomer concentration suggested that both β-Me transfer (major) and β-hydrogen transfer (β-H transfer) (minor) mediated by 5/MMAO and 6/MMAO systems may mainly operate in a bimolecular pathway.
- Metallocene,
- Ethylene-bridged indenyl-fluorenyl ligand,
- Propylene,
- Oligo-/polymerization,
- β-Methyl transfer
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