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Authors
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Tkachov, R. ; Senkovskyy, V. ; Beryozkina, T. ; Boyko, K. ; Bakulev, V. ; Lederer, A. ; Sahre, K. ; Voit, B. ; Kiriy, A.
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Title
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Palladium-catalyzed chain-growth polycondensation AB-type monomers: High catalyst turnover and polymerization rates
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Date
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24.02.2014
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Number
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41923
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Abstract
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Chain-growth catalyst-transfer polycondensations of AB-type monomers is a new and rapidly developing tool for the preparation of well-defined p-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.
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Publisher
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Angewandte Chemie - International Edition
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Wikidata
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Citation
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Angewandte Chemie - International Edition 53 (2014) 2402-2407
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DOI
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https://doi.org/10.1002/anie.201310045
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Tags
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chain growth conjugated polymers homogeneous catalysis palladium polycondensation preferential oxidative addition cross-coupling reactions suzuki polycondensation conjugated polymers molecular design universal method aryl polyfluorene copolymers ligands
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