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Syntheses, crystal structures of a series of copper(II) complexes and their catalytic activities in the green oxidative coupling of 2,6-dimethylphenol
Authors:Erpeng Zhang  Huayun Han
Institution:a Department of Chemistry, Zhengzhou University, Zhengzhou 450052, PR China
b State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, PR China
Abstract:Three mixed-ligand CuII complexes bearing iminodiacetato (ida) and N-heterocyclic ligands, namely, Cu2(ida)2(bbbm)(H2O)2] · H2O (1), Cu2(ida)2(btx)(H2O)2] · 2H2O (2) and Cu2(ida)2(pbbm)(H2O)2] · H2O · 3CH3OH (3) (bbbm = 1,1-(1,4-butanediyl)bis-1H-benzimidazole, btx = 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene, pbbm = 1,1-(1,3-propanediyl)bis-1H-benzimidazole), in addition to three fcz-based CuII complexes, namely, {Cu(fcz)2(H2O)2] · 2NO3}n (4), {Cu(fcz)2(H2O)] · SO4 · DMF · 2CH3OH · 2H2O}n (5) and {Cu(fcz)2Cl2] · 2CH3OH}n (6) (fcz = 1-(2,4-difluorophenyl)-1,1-bis(1H-1,2,4-triazol-l-yl) methyl]ethanol) have been prepared according to appropriate synthetic strategies with the aim of exploiting new and potent catalysts. Single crystal X-ray diffraction shows that 1 and 2 possess similar binuclear structures, 3 features a 2D pleated network, and 4 exhibits a 1D polymeric double-chain structure. Complexes 1-6 are tested as catalysts in the green catalysis process of the oxidative coupling of 2,6-dimethylphenol (DMP). Under the optimized reaction conditions, these complexes are catalytically active by showing high conversion of DMP and high selectivity of PPE. The preliminary study of the catalytic-structural correlations suggests that the coordination environment of the copper center have important influences on their catalytic activities.
Keywords:Copper(II) complexes  Crystal structures  Green catalysis  Oxidative coupling  Catalytic-structural correlation
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