Synthesis and applications of polyvinylpyridine-grafted silica containing palladium nanoparticles as a new heterogeneous catalyst for heck and suzuki coupling reactions

Abstract

A new catalytic system based on palladium nanoparticles supported on poly(4-vinylpyridine) (P4VPy)-grafted silica is introduced. Aminopropylsilica was reacted with acryloyl chloride to form acrylamidopropylsilica. Onto this functionalized silica, 4-vinylpyridine monomer was polymerized by free radical polymerization. The P4VPy-grafted silica was characterized by FT-IR spectroscopy and the amount of (P4VPy) grafted was determind by thermogravimetric analysis (TGA). The complexation of (P4VPy)-grafted silica with Pd(Cl)2 was carried out to obtain the heterogeneous catalytic system. Transmission electron microscopy images (TEM) showed that palladium dispersed through polymer surface in nanoparticle size. This catalytic system exhibited excellent activity in cross-coupling reactions of aryl iodides, bromides and also chlorides, with olefinic compounds in Heck-Mizoraki, and with benzylbronic acid in Suzuki-Miyaura reactions. The use of aryl chlorides in cross-coupling reactions is usually hardly successful, but excellent results were gained in the presence of terta-n-butylammonium bromide (TBAB) as an additive. The turnover number (TON) of this catalyst reaches up to 9 × 104 in these C-C bond forming reactions. High efficiency of the catalyst along with short reaction time, high yields, easy purification, recyclability, large scale synthesis and simple procedure are among the advantages of this catalytic system