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Development of dipyridine‐based coordinative polymers for reusable heterogeneous catalysts
Authors:Hsiang‐Chun Chang  Jia‐Qi Li  Ching‐Kai Lin  Yu‐Jung Hsu  Tsung‐Han Tu  Yi‐Liang Hsieh  Hsiu‐Hao Hsu  Gene‐Hsiang Lee  Yi‐Hung Liu  Chi‐How Peng
Abstract:Poly(di(pyridin‐2‐yl)methyl acrylate) (PDPyMA), which was obtained by the free radical polymerization of designed coordinative monomer of di(pyridin‐2‐yl)methyl acrylate, is able to coordinate with various metal ions to form heterogeneous catalysts for diverse catalytic reactions. The Pd and Cu complexes supported by PDPyMA were developed for the heterogeneous Suzuki‐Miyaura reaction and Friedel‐Crafts alkylation, respectively. The PDPyMA‐based catalysts showed no significant decline of reactivity after five times recycling. However, the hydrolysis of the PDPyMA backbone under alkaline conditions limited the catalytic efficiency of this heterogeneous catalyst so that the coordinative monomer was redesigned as 1,1‐di(pyridine‐2‐yl)‐2‐(4‐vinylphenyl)ethan‐1‐ol and then 2,2′‐(1‐methoxy‐2‐(4‐vinylphenyl)ethane‐1,1‐diyl)dipyridine (MVPhDPy). With copolymerization of N‐isopropyl acrylamide (NIPAM), the efficiency of polymer‐based heterogeneous catalysts could be further raised, demonstrated by the increased turn over number in the Suzuki‐Miyaura reaction, which approached 5,260 by using the catalyst formed from poly(MVPhDPy‐co‐NIPAM) and Pd(OAc)2. poly(MVPhDPy‐co‐NIPAM) copolymer, therefore, could be a versatile platform to support different metal ions for various heterogeneous catalytic reactions.
Keywords:coordinative polymer  heterogeneous catalyst  reusable catalyst
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