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Palladium‐Catalyzed Chain‐Growth Polycondensation of AB‐type Monomers: High Catalyst Turnover and Polymerization Rates |
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| Authors: | Dr Roman Tkachov Dr Volodymyr Senkovskyy Dr Tetyana Beryozkina Dr Kseniya Boyko Prof?Dr Vasiliy Bakulev Dr Albena Lederer Dr Karin Sahre Prof?Dr Brigitte Voit Dr Anton Kiriy |
| Institution: | 1. Leibniz Institute of Polymer Research Dresden, Hohe Stra?e 6, 01069 Dresden (Germany);2. NOVALED AG, Tatzberg 49, 01307 Dresden (Germany);3. TOSLab, Ural Federal University named after the first President of Russia, B.?N. Yeltsin, Mira str., 28, 620002, Yekaterinburg (Russia);4. Organic Chemistry of Polymers, Technische Universit?t Dresden, 01062, Dresden (Germany) |
| Abstract: | Chain‐growth catalyst‐transfer polycondensations of AB‐type monomers is a new and rapidly developing tool for the preparation of well‐defined π‐conjugated (semiconducting) polymers for various optoelectronic applications. Herein, we report the Pd/PtBu3‐catalyzed Negishi chain‐growth polycondensation of AB‐type monomers, which proceeds with unprecedented TONs of above 100 000 and TOFs of up to 280 s?1. In contrast, related AA/BB‐type step‐growth polycondensation proceeds with two orders of magnitude lower TONs and TOFs. A similar trend was observed in Suzuki‐type polycondensation. The key impact of the intramolecular (vs. intermolecular) catalyst‐transfer process on both polymerization kinetics and catalyst lifetime has been revealed. |
| Keywords: | chain growth conjugated polymers homogeneous catalysis palladium polycondensation |