Microflowers formed by complexation-driven self-assembly between palladium(ii) and bis-theophyllines: immortal catalyst for C–C cross-coupling reactions

Abstract

The Pd catalyst for Suzuki–Miyaura or the other C–C coupling reactions is one of the central tools in organic synthesis related to medicine, agricultural chemicals and advanced materials. However, recycling palladium is a bottleneck for developing the extreme potential of Pd in chemistry. Herein, we established a new heterogeneous Pd catalytic system in which the catalyst is a nanopetal-gathered flower-like microsphere self-assembled from PdCl₂ and alkyl-linked bis-theophyllines. The microflowers catalyzed quantitatively the reaction of aryl bromides and phenylboronic acid in aqueous media at room temperature. It was found that the reaction proceeds better in an air atmosphere than in nitrogen gas even though the Pd(II) species employed was lowered to 0.001 mol% in the substance. Very interestingly, the microflowers could be recycled 20 times without deactivation in the C–C coupling reaction between bromobenzene and phenylboronic acid in the presence of sodium chloride. We found that the sodium chloride added played an important role in maintaining the morphology of microflowers and preventing the formation of metallic Pd particles.