Cited by 51Organometallic Complex Synthesis and Catalysisbiodegradable polymer synthesis and propertiesOrganoboron and organosilicon chemistry

ansa-Bis(fluorenyl)neodymium Catalysts for Cyclocopolymerization of Ethylene with Butadiene

Thuilliez, Julien, Ricard, Louis, Nief, François, Boisson, Fernande, Boisson, Christophe·2009·Macromolecules

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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Crossref · 10.1021/ma9003852

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Authors
Thuilliez, J., Ricard, L., Nief, F., Boisson, F., & Boisson, C.
Affiliations
Lyon 1 Université (FR)
Corresponding author
Boisson, Christophe
Venue
Macromolecules
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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