Cited by 47Organometallic Complex Synthesis and CatalysisCyclopropane Reaction MechanismsAdvanced Polymer Synthesis and Characterization

E Stereoregular 1,1 and 1,3 Constitutional Units from 1,3-Butadiene in Copolymerizations Catalyzed by a Highly Hindered C2 Symmetric Metallocene

Longo, Pasquale, Pragliola, Stefania, Milano, Giuseppe, Guerra, Gaetano·2003·Journal of the American Chemical Society

Abstract

Unprecedented 1,1 and 1,3 constitutional units from 1,3-butadiene, both presenting only the E configuration of the double bond, have been achieved by copolymerization with ethene, conducted at high temperature and low ethene concentration, when catalyzed by a highly hindered C(2) symmetric metallocene. Ethene/butadiene copolymerizations by this catalyst generally lead to prevailing methylene-1,2-cyclopropane units from butadiene. Polymer microstructures obtained for different comonomer concentrations clearly indicate that the rate-determining step leading to cyclopropanation involves ethene, while that leading to 1,1 and 1,3 constitutional units does not. A general copolymerization scheme and a molecular modeling study of the cyclopropanation reaction are presented. Molecular modeling also indicates that the E stereoselectivity for 1,1 and 1,3 constitutional units can be rationalized, in the assumption that an allyl isomerization of the terminal of the growing chain would occur.

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Crossref · 10.1021/ja028462v

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Authors
Longo, P., Pragliola, S., Milano, G., & Guerra, G.
Affiliations
University of Salerno (IT)
Venue
Journal of the American Chemical Society
Published
2003-03-26
Volume
125
Issue
16
Pages
4799-4803
ISSN
  • 0002-7863 (ISSN-L)
  • 1520-5126
OpenAlex
W2069346922
Cited by
47
References
34
Citations by year
2025: 3 · 2024: 2 · 2023: 2 · 2022: 1 · 2021: 1 · 2019: 1 · 2018: 1 · 2017: 5 · 2015: 6 · 2013: 1 · 2012: 1
FWCI
2.82
Type
journal article
Language
en
Open access
closed
Locations
  • Journal of the American Chemical Society (publishedVersion)
  • PubMed (publishedVersion)
Topics
  • Physical Sciences › Chemistry › Organic Chemistry › Organometallic Complex Synthesis and Catalysis
  • Physical Sciences › Chemistry › Organic Chemistry › Cyclopropane Reaction Mechanisms
  • Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
Keywords
1,3-butadiene, E-stereoselectivity, cyclopropanation, polymer microstructure, rate-determining step, copolymerization mechanism, molecular modeling

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