Palladium‐Catalyzed Chain‐Growth Polycondensation of AB‐type Monomers: High Catalyst Turnover and Polymerization Rates1. (12th February 2014)

• Record Type: Journal Article
• Authors: Tkachov, Roman; Senkovskyy, Volodymyr; Beryozkina, Tetyana; Boyko, Kseniya; Bakulev, Vasiliy; Lederer, Albena; Sahre, Karin; Voit, Brigitte; Kiriy, Anton
• Is Part Of: Angewandte Chemie. Volume 126:Number 9(2014)
• Page Start: 2434
• Page End: 2439
• Publication Date: 2014-02-12
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201310045
• Languages: English
• ISSNs: 0044-8249

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>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/P<italic>t</italic>Bu₃‐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.</p> </abstract>