ansa-Bis(fluorenyl)neodymium Catalysts for Cyclocopolymerization of Ethylene with Butadiene
Abstract
Metallocene borohydride complexes {(Me 2 Si(C 13 H 8 ) 2 )Nd(μ-BH 4 )[(μ-BH 4 )Li(THF)]} 2 ( 1 ) and (Me 2 Si(2,7- t Bu 2 C 13 H 6 ) 2 )Nd(BH 4 )(μ-BH 4 )Li(ether) 3 ( 2 ) were prepared by reaction of the dilithium salts of silylene-bridged bis(fluorenyl) ligands with the borohydride precursor Nd(BH 4 ) 3 (THF) 3 . The solid state structures of dimeric 1 and monomeric 2 ate complexes were established by X-ray diffraction studies. We showed that these complexes used in combination with ( n Bu)( n Oct)Mg are highly efficient for cyclocopolymerization of ethylene with butadiene leading to a new class of elastomers. Catalyst 1 /( n Bu)( n Oct)Mg provided elastomers with a polyethylene skeleton incorporating unsaturated groups (trans double bond and pendant vinyl units) and 1,2-cyclohexane rings. These rings are formed via an intramolecular cyclization which occurs with a high trans selectivity. The investigation of catalyst 2 /( n Bu)( n Oct)Mg has revealed that the tertio-butyl substitution in positions 2 and 7 of fluorenyl ligands influenced the microstructure of copolymers since in addition to 1,2-cyclohexane rings, 1,4-cyclohexane rings were formed. This original microstructure was characterized using 2D NMR 1 H− 1 H and 1 H− 13 C with direct and long-range correlations. Mechanisms of stereoselective formation of trans -1,2-cyclohexane and trans -1,4-cyclohexane rings were fully investigated.
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- Authors
- Thuilliez, J., Ricard, L., Nief, F., Boisson, F., & Boisson, C.
- Affiliations
- Lyon 1 Université (FR)
- Corresponding author
- Boisson, Christophe
- ORCID
- Boisson, Christophe
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2009-04-20
- Volume
- 42
- Issue
- 11
- Pages
- 3774-3779
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W1982230511
- Cited by
- 51
- References
- 44
- Citations by year
- 2026: 1 · 2025: 3 · 2024: 7 · 2023: 5 · 2022: 3 · 2021: 3 · 2020: 2 · 2019: 4 · 2018: 4 · 2017: 4 · 2015: 3 · 2014: 1 · 2013: 3 · 2012: 3
- FWCI
- 1.29
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Macromolecules (publishedVersion)
- HAL (submittedVersion)
- Topics
- Physical Sciences › Chemistry › Organic Chemistry › Organometallic Complex Synthesis and Catalysis
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Chemistry › Organic Chemistry › Organoboron and organosilicon chemistry
- Keywords
- cyclocopolymerization, intramolecular cyclization, trans-selectivity, elastomers, copolymer microstructure
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