title: Multifunctional Single-Site Catalysts for Alkoxycarbonylation of Terminal Alkynes.
abstract: A multifunctional copolymer (PyPPh2 -SO3 H@porous organic polymers, POPs) was prepared by combining acidic groups and heterogeneous P,N ligands through the copolymerization of vinyl-functionalized 2-pyridyldiphenylphosphine (2-PyPPh2 ) and p-styrene sulfonic acid under solvothermal conditions. The morphology and chemical structure of the copolymer were evaluated using a series of characterization techniques. Compared with traditional homogeneous Pd(OAc)2 /2-PyPPh2 / p-toluenesulfonic acid catalyst, the copolymer supported palladium catalyst (Pd-PyPPh2 -SO3 H@POPs) exhibited higher activity for alkoxycarbonylation of terminal alkynes under the same conditions. This phenomenon could be attributed to the synergistic effect between the single-site Pd centers, 2-PyPPh2 ligands, and SO3 H groups, the outstanding swelling properties as well as the high enrichment of the reactant concentration by the porous catalyst. In addition, the catalyst could be reused at least 4 times without any apparent loss of activity. The excellent catalytic reactivity and good recycling properties make it an attractive catalyst for industrial applications. This work paves the way for advanced multifunctional porous organic polymers as a new type of platform for heterogeneous catalysis in the future.
authors.affiliation: Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian, 116023, China.|University of Chinese Academy of Sciences, Beijing, 100049, China.
authors.forename: Xingkun
authors.initials: X
authors.lastname: Chen
authors.affiliation: Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian, 116023, China. zhuhj@dicp.ac.cn.
authors.forename: Hejun
authors.initials: H
authors.lastname: Zhu
authors.affiliation: Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian, 116023, China.
authors.forename: Wenlong
authors.initials: W
authors.lastname: Wang
authors.affiliation: Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian, 116023, China.|University of Chinese Academy of Sciences, Beijing, 100049, China.
authors.forename: Hong
authors.initials: H
authors.lastname: Du
authors.affiliation: Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian, 116023, China.|University of Chinese Academy of Sciences, Beijing, 100049, China.
authors.forename: Tao
authors.initials: T
authors.lastname: Wang
authors.affiliation: Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian, 116023, China.
authors.forename: Li
authors.initials: L
authors.lastname: Yan
authors.affiliation: Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian, 116023, China.
authors.forename: Xiangping
authors.initials: X
authors.lastname: Hu
authors.affiliation: Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian, 116023, China. dyj@dicp.ac.cn.|The State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian, 116023, China. dyj@dicp.ac.cn.
authors.forename: Yunjie
authors.initials: Y
authors.lastname: Ding
mesh_terms: D000480:Alkynes / Q000737:chemistry*; D002384:Catalysis; D010720:Phosphines / Q000737:chemistry*; D058105:Polymerization; D016062:Porosity
chemical_list: D000480:Alkynes; D010720:Phosphines
keywords: alkoxycarbonylation; multifunctional catalyst; palladium; porous organic polymers; solid acid