[en] Cobalt-mediated radical coupling (CMRC) is a straightforward approach to the synthesis of symmetrical macromolecules that relies on the addition of 1,3-diene compounds onto polymer precursors preformed by cobalt-mediated radical polymerization (CMRP). Mechanistic features that make this process so efficient for radical polymer coupling are reported here. The mechanism was established on the basis of NMR spectroscopy and MALDI-MS analyses of the coupling product and corroborated by DFT calculations. A key feature of CMRC is the preferential insertion of two diene units in the middle of the chain of the coupling product mainly according to a trans-1,4-addition pathway. The large tolerance of CMRC towards the diene structure is demonstrated and the impact of this new coupling method on macromolecular engineering is discussed, especially for midchain functionalization of polymers. It is worth noting that the interest in CMRC goes beyond the field of polymer chemistry, since it constitutes a novel carbon-carbon bond formation method that could be applied to small organic molecules.
Research Center/Unit :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Chemistry Materials science & engineering
Author, co-author :
Debuigne, Antoine ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Poli, Rinaldo; University of Toulouse and Institut Universitaire de France (Paris) > Laboratoire de Chimie de Coordination (Toulouse)
De Winter, Julien; University of Mons (UMons) > Mass Spectrometry Center, Organic Chemistry Laboratory
Laurent, Pascal ; Université de Liège - ULiège > Chimie et bio-industries > Chimie biologique industrielle
Gerbaux, Pascal; University of Mons (UMons) > Mass Spectrometry Center, Organic Chemistry Laboratory
Dubois, Philippe; University of Mons (UMons) > Center of Innovation and Research in Materials and Polymers (CIRMAP), Laboratory of Polymeric and Composite Materials (SMPC)
Wathelet, Jean-Paul ; Université de Liège - ULiège > Chimie et bio-industries > Chimie générale et organique
Jérôme, Christine ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Detrembleur, Christophe ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Language :
English
Title :
Cobalt mediated radical coupling (CMRC) : an unusual route to midchain-functionalized symmetrical macromolecules
BELSPO - SPP Politique scientifique - Service Public Fédéral de Programmation Politique scientifique F.R.S.-FNRS - Fonds de la Recherche Scientifique The french "CNRS" and the IUF
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