Microporous dinuclear copper(II) trans-1,4-cyclohexanedicarboxylate: heterogeneous oxidation catalysis with hydrogen peroxide and X-ray powder structure of peroxo copper(II) intermediate
Microporous dinuclear copper(II) trans-1,4-cyclohexanedicarboxylate: heterogeneous oxidation catalysis with hydrogen peroxide and X-ray powder structure of peroxo copper(II) intermediate
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DOI：
10.1016/j.jcat.2004.11.032
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发表时间：
2005-02
影响因子：
7.3
通讯作者：
C. Kato;M. Hasegawa;Tomohiko Sato;Akira Yoshizawa;Tomonori Inoue;W. Mori
中科院分区：
文献类型：
--
作者：
C. Kato;M. Hasegawa;Tomohiko Sato;Akira Yoshizawa;Tomonori Inoue;W. Mori
二维微孔双核反式1,4-环己烷二甲酸铜(II) [CuII,II2(OOCC6H10COO)2]⋅H2O (1) 可作为多相催化剂，用于过氧化氢选择性氧化各种醇。配合物 1 在非均相体系中催化 2-丙醇、环己醇、苯甲醇、2-辛醇和 1-辛醇的选择性氧化，选择性 >99%。在 1 与乙腈中 20 倍过量的 H2O2 反应中观察到的绿色活性中间体 H2[CuII,II2(OOCC6H10COO)2(O2)]⋅H2O (2) 通过元素分析、TG/DTA、磁化率、FT-IR、漫反射 UV-vis、EPR、X 射线粉末衍射 (XRPD)、共振拉曼光谱、BET 进行表征表面积、孔径分布和氮吸留测量。 2的分子结构由XRPD数据确定并通过Rietveld方法精修。 2的微孔结构是通过二维[Cu2(O2CC6H10CO2)]层之间μ-1,2-反式CuOOCu物质的分子内桥联构建的。配合物2是用于多相氧化催化的微孔过氧铜(II)配合物的第一个例子。
A two-dimensional microporous dinuclear copper(II) trans-1,4-cyclohexanedicarboxylate, [CuII,II2(OOCC6H10COO)2]⋅H2O (1), can act as a heterogeneous catalyst for selective oxidations of various alcohols with hydrogen peroxide. Complex 1 catalyzed the selective oxidations of 2-propanol, cyclohexanol, benzyl alcohol, 2-octanol, and 1-octanol with >99% selectivities in a heterogeneous system. A green-colored active intermediate, H2[CuII,II2(OOCC6H10COO)2(O2)]⋅H2O (2), observed in the reaction of 1 with a 20-fold excess H2O2in acetonitrile was characterized by elemental analysis, TG/DTA, magnetic susceptibility, FT-IR, diffuse reflectance UV–vis, EPR, X-ray powder diffraction (XRPD), resonance Raman spectra, BET surface area, pore size distribution, and nitrogen occlusion measurements. The molecular structure of 2 was determined from XRPD data and refined by the Rietveld method. The microporous structure of 2 was constructed by intramolecular bridging of μ-1,2-trans CuOOCu species between two-dimensional [Cu2(O2CC6H10CO2)] layers. The complex 2 was the first example of the microporous copper(II) peroxo complex for heterogeneous oxidation catalysis.