AmPhos Pd-Catalyzed Suzuki–Miyaura Catalyst-Transfer Condensation Polymerization: Narrower Dispersity by Mixing the Catalyst and Base Prior to Polymerization

Kentaro Kosaka, Tatsuya Uchida, Koichiro Mikami, Tsutomu Yokozawa, Yoshihiro Ohta

doi:10.1021/acs.macromol.7b01990

Several palladium catalysts with bulky phosphine ligands other than t-Bu3P were investigated for Suzuki–Miyaura catalyst-transfer condensation polymerization (CTCP). When the model reaction of 2,5-dibromothiophene with phenylboronic acid ester was carried out with a variety of Pd precatalysts in the presence of K3PO4 as a base, we found that the use of di-tert-butyl(4-dimethylaminophenyl)phosphine (AmPhos) Pd as a precatalyst resulted in exclusive formation of diphenyl-substituted thiophene. Polymerization of thiophene monomer and fluorene monomer with an initiator generated in situ from AmPhos Pd precatalyst and 4-iodobenzonitrile proceeded via the CTCP mechanism, affording polythiophene (P3HT) and polyfluorene with low dispersity and controlled polymer ends. Furthermore, (tolyl)PdAmPhos(Br) (7) was synthesized, and its polymerization properties were investigated. We found that polymerization of thiophene monomer with a mixture of 7 and CsF that had been stirred for 1 h prior to polymerization afforded P...

AmPhos Pd-Catalyzed Suzuki–Miyaura Catalyst-Transfer Condensation Polymerization: Narrower Dispersity by Mixing the Catalyst and Base Prior to Polymerization

Bibliographic Information

Search this article

Description

Journal

Citations (5)*help

References(39)*help

Related Projects

Details 詳細情報について

Export

Report a problem