Polystyrene microsphere-immobilized palladium(II) porphyrin as mild, reusable, and highly efficient catalyst for Heck reaction--颗粒学报PARTICUOLOGY

Huang, Y., Yang, L., Huang, M., Wang, J., Xu, L., Li, W., . . . Liu, H. (2015). Polystyrene microsphere-immobilized palladium(II) porphyrin as mild, reusable, and highly efficient catalyst for Heck reaction. Particuology, 22, 128-133. https://doi.org/10.1016/j.partic.2014.08.003

Polystyrene microsphere-immobilized palladium(II) porphyrin as mild, reusable, and highly efficient catalyst for Heck reaction

Yinbin Huang ^{a b}, Liangrong Yang ^a *, Minghui Huang ^c, Jian Wang ^a, Lin Xu ^a, Wensong Li ^a, Huacong Zhou ^a, Xitong Sun ^a, Huifang Xing ^a, Huizhou Liu ^{a *}

a Key Laboratory of Green Processes and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
b Agricultural & Biosystems Engineering, South Dakota State University, Brookings, SD 57006, USA
c Art College, Hubei University of Economics, Jiangxia District, Wuhan 430205, China

10.1016/j.partic.2014.08.003

Volume 22, October 2015, Pages 128-133

Received 17 June 2014, Revised 31 July 2014, Accepted 13 August 2014, Available online 12 November 2014, Version of Record 4 August 2015.

E-mail: lryang@home.ipe.ac.cn; hzliu@home.ipe.ac.cn

Highlights

• A palladium(II) porphyrin complex was successfully immobilized on PMs surfaces.

• The Pd-MTP/PMs catalyst gave higher GC yield in Heck reaction of iodobenzene with ethyl acrylate.

• The catalyst showed better reusability with no Pd leaching in the Heck reaction.

Abstract

A novel Heck reaction catalyst consisting of a palladium(II) complex of meso-tetra(p-hydroxyphenyl)porphyrin (MTP) and cross-linked chloromethylated polystyrene microspheres (PMs) was successfully prepared via covalent ether bonds between the chloride groups in the PMs and the hydroxyl groups in MTP. The catalyst was characterized using scanning electron microscopy, Fourier-transform infrared spectroscopy, and inductively coupled plasma atomic emission spectroscopy (ICP-AES). This polystyrene-supported palladium-complex was an efficient heterogeneous catalyst for cross-coupling of aryl iodides with ethyl acrylate. The reaction of iodobenzene and ethyl acrylate under N₂ at 100 °C and a catalyst concentration of 0.1% gave a gas chromatography product yield of 99.8%, which is much higher than that achieved using a free palladium(II) complex of MTP as the catalyst (41.3%). The catalyst was recycled up to six times without significant loss of catalytic activity. These results suggest that the immobilized palladium(II)–MTP catalyst has potential applications in synthetic and industrial chemistry.

Graphical abstract

Keywords

Heterogeneous catalyst; Palladium–porphyrin; Polystyrene microspheres; Heck reaction

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