Recyclable heterogeneous palladium-catalyzed carbon–carbon coupling polycondensations toward highly purified conjugated polymers

Conjugated polymers are usually synthesized by homogeneous palladium complexes-catalyzed Heck, Suzuki, and Stille coupling reactions, which suffer from the non- recyclability of expensive palladium catalysts and palladium contamination of the desired polymer due to palladium leaching. In order to overcome these drawbacks, a bidentate phosphino-modified magnetic nanoparticles-anchored palladium complex (PdCl2-Fe3O4@SiO2-2P) as a clean and efficient heterogeneous catalyst for the carbon–carbon coupling polycondensations was developed in present work. The PdCl2-Fe3O4@SiO2-2P catalyst exhibited an enhanced catalytic activity for Heck, Suzuki, and Stille coupling polymerizations, as compared with the most commonly used homogeneous Pd(PPh3)4. Moreover, this heterogeneous palladium catalyst showed advantage of much less palladium impurity (below 13 ppm) in the isolated polymers. Importantly, PdCl2-Fe3O4@SiO2-2P can facilely be separated from the reaction products and recovered by using an external magnetic field, and recycled at least eight times with almost consistent catalytic activity.