[en] Pd(RuPhos) has recently been introduced as an external initiator for Suzuki-Miyaura catalyst transfer condensative polymerizations (SMCTCPs), exhibiting a controlled polymerization behavior. Paradoxically, the same initiator also enables a controlled activation-deactivation polymerization, raising questions about how these opposing mechanisms can yield controlled polymerizations. This study investigates key parameters influencing control in SMCTCP using poly(3-hexylthiophene) (P3HT), synthesized with a bench-stable, isolated external Pd(RuPhos) initiator, thereby elucidating why these two mechanisms can result in a controlled polymerization behavior. Our results demonstrate that increasing the water content reduces chain transfer reactions in the presence of a chain transfer agent (CTA). Alternative cosolvents, including 1-hexanol and anisole, are explored to mitigate water's other adverse effects, showing a similar beneficial impact, though complete control remains challenging. Introducing additional RuPhos significantly reduces transfer reactions, producing P3HT with a dispersity of 1.16 compared to 1.28 without additional ligand, indicating improved control even with CTA present. The controlled nature of the polymerization is further validated through 1H NMR and MALDI-ToF analyses. A 31P NMR study reveals that free RuPhos forms in the absence of additional ligand, compromising control during polymerization. A computational survey of the coordination environment of the catalytic palladium species and the measurement of reaction rates strongly suggest that water and RuPhos act synergistically: water stabilizes the Pd(RuPhos)-polymer complex via a solvent cage, while additional RuPhos prevents diffusion of the Pd(RuPhos) complex. These findings reconcile the disparate mechanisms of SMCTCP and activation-deactivation polymerization, highlighting the critical roles of water and RuPhos in controlling transfer reactions.
Disciplines :
Chemistry
Author, co-author :
Detavernier, Siebe; Laboratory for Polymer Synthesis, KU Leuven, Heverlee, Belgium
Matz, Florian; Quantum Chemistry and Physical Chemistry, KU Leuven, Heverlee, Belgium
De Winter, Julien ; Organic Synthesis and Mass Spectrometry Laboratory, Center of Innovation and Research in Materials and Polymers (CIRMAP) – University of Mons (UMONS), Mons, Belgium
Gerbaux, Pascal ; Université de Mons - UMONS > Faculté des Sciences > Service de Synthèse et spectrométrie de masse organiques
Jagau, Thomas-C.; Quantum Chemistry and Physical Chemistry, KU Leuven, Heverlee, Belgium
Koeckelberghs, Guy; Laboratory for Polymer Synthesis, KU Leuven, Heverlee, Belgium
Language :
English
Title :
Towards control in Suzuki-Miyaura CTCP – the synergy between water and RuPhos
Research Institute for Materials Science and Engineering
Funding text :
This research was funded by the Fund for Scientific Research (FWO-Flanders - 1SB1623N ) and by Onderzoeksfonds KU Leuven/Research Fund KU Leuven. S.D. is doctoral fellow of the Fund for Scientific Research (FWO-Flanders).This research was supported by the Research Foundation Flanders (FWO) through infrastructure grant I002720N.
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