Cobalt–oxygen bond homolysis in the bench-sable (Salen*)cobalt(III) acetate complex: insight into the organometallic mediated radical polymerization of diverse monomers
[en] ABSTRACTThermal activation of the [(Salen*)CoIII(OAc)] (Salen* = (R,R)‐N, N’‐bis(3,5‐di‐tert‐butylsalicylidene)‐1,2‐cyclohexanediamine) complex (1) allows to initiate the radical polymerization of methyl methacrylate (MMA) and methyl acrylate (MA) via CoIII─O bond homolysis. Catalytic chain‐transfer has been identified as the dominant mechanism in the case of MMA, leading predominantly to α‐H and ω‐unsaturated polymeric chains, as deduced from MALDI‐ToF mass spectrometry (MS). In contrast, the organometallic‐mediated radical polymerization (OMRP) of MA is well‐controlled, and the pseudo‐livingness of the process could be highlighted by a linear increase of poly(methyl acrylate) (PMA) molar mass with the conversion, low dispersities, and the successful chain‐extension of a CoIII‐capped PMA macroinitiator with n‐butyl acrylate (BA), leading to a well‐defined poly(methyl acrylate)‐block‐poly(n‐butyl acrylate) (PMA‐b‐PBA) block copolymer. MALDI‐ToF MS and multinuclear NMR analyses allowed to identify two competing initiation processes for the OMRP of MA.
Research Center/Unit :
CESAM - Complex and Entangled Systems from Atoms to Materials - ULiège [BE] CERM - Center for Education and Research on Macromolecules - ULiège [BE]
Disciplines :
Materials science & engineering Chemistry
Author, co-author :
Michelas, Maxime; Université de Toulouse [UPS] - CNRS - Laboratoire de Chimie de Coordination [LCC] - Institut National Polytechnique [INPT] - Toulouse - France
McGee‐Renedo, Sofia; University of Liège [ULiège] - Complex and Entangled Systems from Atoms to Materials [CESAM] Research Unit - Center for Education and Research on Macromolecules [CERM] - Belgium
Wang, Jirong; Université de Toulouse [UPS] - CNRS - Laboratoire de Chimie de Coordination [LCC] - Institut National Polytechnique [INPT] - Toulouse - France
Poli, Rinaldo; Université de Toulouse [UPS] - CNRS - Laboratoire de Chimie de Coordination [LCC] - Institut National Polytechnique [INPT] - Toulouse - France ; Institut Universitaire de France - Paris - France
Debuigne, Antoine ; University of Liège [ULiège] - Complex and Entangled Systems from Atoms to Materials [CESAM] Research Unit - Center for Education and Research on Macromolecules [CERM] - Belgium
Fliedel, Christophe ; Université de Toulouse [UPS] - CNRS - Laboratoire de Chimie de Coordination [LCC] - Institut National Polytechnique [INPT] - Toulouse - France
Language :
English
Title :
Cobalt–oxygen bond homolysis in the bench-sable (Salen*)cobalt(III) acetate complex: insight into the organometallic mediated radical polymerization of diverse monomers
Publication date :
2025
Journal title :
Macromolecular Chemistry and Physics
ISSN :
1022-1352
eISSN :
1521-3935
Publisher :
Wiley
Volume :
226
Issue :
18
Pages :
202500204
Peer reviewed :
Peer Reviewed verified by ORBi
Funders :
F.R.S.-FNRS - Fund for Scientific Research CNRS - French National Centre for Scientific Research ANR - French National Research Agency
Funding text :
The authors gratefully acknowledge funding by the ANR (Agence Nationale de la Recherche) through the POLYSWITCH project (grant ANR-19-CE07-0031-01) and by the CNRS (Centre National de la Recherche Scientifique). R.P. is also grateful to theCALMIPmesocenter of the University of Toulouse for the allocation of computational resources. A.D. is FNRSSeniorResearch Associate and is grateful to the F.R.S.-FNRS. The authors thank ZhuoqunWang for the fruitful discussions and for her help in setting up some experiments and Jadhe Salin for performing some polymerization reactions and GPC analyses.
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