Activation of Nitromethane to Cyanide by a Mononuclear Cu(Ⅱ) Complex  

作　　者：吴楠楠 陈昌能 黄德光 

机构地区：[1]State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences [2]University of Chinese Academy of Sciences

出　　处：《Chinese Journal of Structural Chemistry》2014年第11期1643-1648,共6页结构化学（英文）

基　　金：granted by the National Natural Science Foundation of China(No.21371171)

摘　　要：The tridentate ligand DPA-Me（2） was readily prepared from DPA（DPA = 2,2-dipicolylamine） in high yield. The mixture of 2 and Cu（ClO4）26H2O in methanol gave a five-coordinated mononuclear complex [（DPA-Me）Cu（Me CN）（ClO4）]（ClO4）（3）. Recrystallization of 3 in CH3NO2 led to an activation of CH3NO2 to CN- by the formation of product as a dinuclear cyanide bridged complex {[Cu（DPA-Me）]2（CN）（ClO4）3CH3NO2}n（4）. Both 3 and 4 were characterized by X-ray crystallography, IR spectroscopy and elemental analysis. The crystal of 4 was grown in space group P21/c with a = 17.74582（15）, b = 13.89877（11）, c = 14.92546（13） A, β = 91.4246（8）°, V = 3680.15（5） 3, Z = 4, Dc = 1.695 g/cm^3, F（000） = 1912, C28H33Cl3Cu2N8O14, Mr = 939.05, μ = 1.602 cm^-1, Cu Kα radiation（λ = 1.54184 ）, R = 0.0485 and w R = 0.1246 for 6414 observed reflections with I 〉 2σ（I）.The tridentate ligand DPA-Me（2） was readily prepared from DPA（DPA = 2,2-dipicolylamine） in high yield. The mixture of 2 and Cu（ClO4）26H2O in methanol gave a five-coordinated mononuclear complex [（DPA-Me）Cu（Me CN）（ClO4）]（ClO4）（3）. Recrystallization of 3 in CH3NO2 led to an activation of CH3NO2 to CN- by the formation of product as a dinuclear cyanide bridged complex {[Cu（DPA-Me）]2（CN）（ClO4）3CH3NO2}n（4）. Both 3 and 4 were characterized by X-ray crystallography, IR spectroscopy and elemental analysis. The crystal of 4 was grown in space group P21/c with a = 17.74582（15）, b = 13.89877（11）, c = 14.92546（13） A, β = 91.4246（8）°, V = 3680.15（5） 3, Z = 4, Dc = 1.695 g/cm^3, F（000） = 1912, C28H33Cl3Cu2N8O14, Mr = 939.05, μ = 1.602 cm^-1, Cu Kα radiation（λ = 1.54184 ）, R = 0.0485 and w R = 0.1246 for 6414 observed reflections with I 〉 2σ（I）.

关 键 词：tridentate ligand COPPER ACTIVATION NITROMETHANE CYANIDE 

分 类 号：O627.12[理学—有机化学]