Leibniz Institute of Polymer Research Dresden, Hohe Straße 6, 01069 Dresden (Germany).
Angew Chem Int Ed Engl. 2014 Feb 24;53(9):2402-7. doi: 10.1002/anie.201310045. Epub 2014 Feb 12.
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.
AB 型单体的链增长催化剂转移缩聚是一种新兴的、快速发展的工具，可用于制备各种光电应用的具有明确结构的π共轭（半导体）聚合物。在此，我们报告了 Pd/PtBu3 催化的 AB 型单体的 Negishi 链增长缩聚，其TON 值空前超过 100,000，TOF 值高达 280 s-1。相比之下，相关的 AA/BB 型逐步缩聚的 TON 值和 TOF 值低两个数量级。在 Suzuki 型缩聚中也观察到了类似的趋势。揭示了分子内（与分子间）催化剂转移过程对聚合动力学和催化剂寿命的关键影响。
