Reference : Key role of intramolecular metal chelation and hydrogen bonding in the cobalt-mediated r...
Scientific journals : Article
Engineering, computing & technology : Materials science & engineering
Physical, chemical, mathematical & earth Sciences : Chemistry
http://hdl.handle.net/2268/129692
Key role of intramolecular metal chelation and hydrogen bonding in the cobalt-mediated radical polymerization of N-vinyl amides
English
Debuigne, Antoine mailto [University of Liège (ULg) > Department of Chemistry > Center for Education and Research on Macromolecules (CERM) > >]
Morin, Aurélie [University of Toulouse, France > > Laboratoire de Chimie de Coordination (LCC) > >]
Kermagoret, Anthony [University of Liège (ULg) > Department of Chemistry > Center for Education and Research on Macromolecules (CERM) > >]
Piette, Yasmine [University of Liège (ULg) > Department of Chemistry > Center for Education and Research on Macromolecules (CERM) > >]
Detrembleur, Christophe mailto [University of Liège (ULg) > Department of Chemistry > Center for Education and Research on Macromolecules (CERM) > >]
Jérôme, Christine mailto [University of Liège (ULg) > Department of Chemistry > Center for Education and Research on Macromolecules (CERM) > >]
Poli, Rinaldo [University of Toulouse and Institut Universitaire de France > > Laboratoire de Chimie de Coordination (LCC) > >]
2012
Chemistry : A European Journal
Wiley
18
12834-12844
Yes (verified by ORBi)
International
0947-6539
1521-3765
[en] radical polymerization ; cobalt-mediated radical polymerization (CMRP)
[en] This work reveals the preponderance of an intramolecular metal chelation phenomenon in a controlled radical polymerization system involving the reversible trapping of the radical chains by a cobalt complex, i.e. the bis(acetylacetonato)cobalt(II). The cobalt-mediated radical polymerization (CMRP) of a series of N-vinyl amides was considered in order to evidence the effect of the cobalt chelation by the amide moiety of the last monomer unit of the chain. The latter reinforces the cobalt-polymer bond in the order N-vinylpyrrolidone < N-vinyl caprolactam < N-methyl-N-vinyl acetamide, and is responsible for the optimal control of the polymerizations observed for the last two monomers. Such a double linkage between the controlling agent and the polymer, via a covalent bond and a dative one, is unique in the field of controlled radical polymerization and represents a powerful opportunity to fine tune the equilibrium between latent and free radicals. The possible hydrogen bond formation is also taken into account in the case of N-vinyl acetamide and N-vinyl formamide. These results are essential for understanding factors influencing a Co-C bond strength in general, and the CMRP mechanism in particular, but also for developing a powerful platform for the synthesis of new precision poly(N-vinyl amide)s, an important class of polymers which sustains numerous applications today.
Center for Education and Research on Macromolecules (CERM)
Fonds de la Recherche Scientifique (Communauté française de Belgique) - F.R.S.-FNRS ; Politique Scientifique Fédérale (Belgique) = Belgian Federal Science Policy ; The Centre National de la Recherche Scientifique (CNRS, France) ; The Institut Universitaire de France (IUF) ; The Agence National de la Recherche
Researchers
http://hdl.handle.net/2268/129692
10.1002/chem.201201456
http://onlinelibrary.wiley.com/doi/10.1002/chem.201201456/abstract

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