Palladium-catalyzed chain-growth polycondensation of AB-type monomers: high catalyst turnover and polymerization rates

Roman Tkachov; Volodymyr Senkovskyy; Tetyana Beryozkina; Kseniya Boyko; Vasiliy Bakulev; Albena Lederer; Karin Sahre; Brigitte Voit; Anton Kiriy

doi:10.1002/anie.201310045

Palladium-catalyzed chain-growth polycondensation of AB-type monomers: high catalyst turnover and polymerization rates

Angew Chem Int Ed Engl. 2014 Feb 24;53(9):2402-7. doi: 10.1002/anie.201310045. Epub 2014 Feb 12.

Authors

Roman Tkachov¹, Volodymyr Senkovskyy, Tetyana Beryozkina, Kseniya Boyko, Vasiliy Bakulev, Albena Lederer, Karin Sahre, Brigitte Voit, Anton Kiriy

Affiliation

¹ Leibniz Institute of Polymer Research Dresden, Hohe Straße 6, 01069 Dresden (Germany).

PMID: 24520053
DOI: 10.1002/anie.201310045

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.