Two Copper Complexes Based on Pyrazole-3-carboxylic Acid as Heterogeneous Catalysts for Highly Selective Oxidation of Alkylbenzenes  

作　　者：蒋秀燕 荣念新 钱瑞 邱田田 姚清侠 黄现强 

机构地区：[1]School of Chemical Engineering, Shengli College, China University of Petroleum [2]Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, School of Chemistry & Chemical Engineering, Liaocheng University

出　　处：《Chinese Journal of Structural Chemistry》2018年第2期329-337,共9页结构化学（英文）

基　　金：supported by the NNSFC(Nos.21401094 and 21501086);the Project of Shandong Province Higher Educational Science and Technology Program(No.J16LC53);the College Students'Science and Technology Innovation Fund(No.CXCY2017028 and CXCY2017037)

摘　　要：Two new copper complexes based on pyrazole-3-carboxylic acid （H2pca） ligand, Cu（Hpca）2（H2O）2？2H2O （1） and Cu2（pca）2（H2O）4 （2） have been synthesized and fully characterized by single-crystal X-ray diffraction （SXRD）, infrared spectroscopy （IR）, thermal gravity analysis （TGA）, powder X-ray diffraction （PXRD） and elemental analyses. Complex 1 is mononuclear while complex 2 shows a dinuclear structure. Complex 1 crystallizes in the monoclinic system, space group P21/c with Z = 2, a = 6.5591（5）, b = 21.696（2）, c = 4.9486（2） ？, V = 680.94（9） ？3, F（000） = 366, Dc = 1.745 g/cm3, μ = 1.650 mm-1, the final R = 0.0340 and wR = 0.0792. Complex 2 crystallizes in the monoclinic system, space group P21/n with Z = 2, a = 5.1935（4）, b = 9.6052（7）, c = 12.7347（9） ？, V = 634.44（8） ？3, F（000） = 420, Dc = 2.195 g/cm3, μ = 3.404 mm-1, the final R = 0.0305 and wR = 0.0653. The three-dimensional frameworks of two complexes are formed by the O？H？？？O and N？H？？？O hydrogen bonding interactions. Notably, two copper complexes are further used as catalysts in the oxidation of alkylbenzenes using t-butylhydroperoxide （TBHP） as the oxidant and they exhibit excellent catalytic performance （Conv. up to 98.9%, Sele. up to 98.7%）.Two new copper complexes based on pyrazole-3-carboxylic acid （H2pca） ligand, Cu（Hpca）2（H2O）2？2H2O （1） and Cu2（pca）2（H2O）4 （2） have been synthesized and fully characterized by single-crystal X-ray diffraction （SXRD）, infrared spectroscopy （IR）, thermal gravity analysis （TGA）, powder X-ray diffraction （PXRD） and elemental analyses. Complex 1 is mononuclear while complex 2 shows a dinuclear structure. Complex 1 crystallizes in the monoclinic system, space group P21/c with Z = 2, a = 6.5591（5）, b = 21.696（2）, c = 4.9486（2） ？, V = 680.94（9） ？3, F（000） = 366, Dc = 1.745 g/cm3, μ = 1.650 mm-1, the final R = 0.0340 and wR = 0.0792. Complex 2 crystallizes in the monoclinic system, space group P21/n with Z = 2, a = 5.1935（4）, b = 9.6052（7）, c = 12.7347（9） ？, V = 634.44（8） ？3, F（000） = 420, Dc = 2.195 g/cm3, μ = 3.404 mm-1, the final R = 0.0305 and wR = 0.0653. The three-dimensional frameworks of two complexes are formed by the O？H？？？O and N？H？？？O hydrogen bonding interactions. Notably, two copper complexes are further used as catalysts in the oxidation of alkylbenzenes using t-butylhydroperoxide （TBHP） as the oxidant and they exhibit excellent catalytic performance （Conv. up to 98.9%, Sele. up to 98.7%）.

关 键 词：copper complexes crystal structure oxidation of alkylbenzenes 

分 类 号：O621.251[理学—有机化学] O641.4[理学—化学]