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

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The tridentate ligand DPA-Me(2) was readily prepared from DPA(DPA = 2,2-dipicolylamine) in high yield. The mixture of 2 and Cu(Cl O4)26H2O in methanol gave a five-coordinated mononuclear complex [(DPA-Me)Cu(Me CN)(Cl O4)](Cl O4)(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)(Cl O4)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) , β = 91.4246(8)°, V = 3680.15(5) 3, Z = 4, Dc = 1.695 g/cm3, 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 mixture of 2 and Cu (ClO4) 26H2O in methanol gave a five-coordinated mononuclear complex [(DPA ​​= 2,2-dipicolylamine) -Me) Cu (MeCN) (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 = 17.74582 (15), b = 13.89877 (11), c = 14.92546 (13), β = 91.4246 (8) °, V = 3680.15 (5) 3, Z = 4, Dc = 1.695 g / cm3, 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 at reflections with I> 2σ (I).
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