Synthesis, Structures and Bonding Properties of bis(2-pyridylmethyl)amine and 2-(2-pyridylethyl)picolylamine of Copper(II) Complexes

• Main Authors: Huang Gin-Song, 黃進松
• Other Authors: Su Chan-Cheng
• Format: Others
• Language: zh-TW
• Published: 1999
• Online Access: http://ndltd.ncl.edu.tw/handle/90326570541937845933

博士 === 國立臺灣師範大學 === 化學研究所 === 87 === Abstract The following Cu(II) complexes have been synthesized: cis-fac-[Cu(dipica)2](ClO4)2, trans-fac-and sq-py-[Cu(dipica)2](ClO4)2, trans-fac-[Cu(pepica)2](ClO4)2, [Cu(pepica)(bipy)](ClO4)2, [Cu(pepica)(phen)](ClO4)2, [Cu(pepica)(neoc)](ClO4)2, [Cu(pepica)(en)](ClO4)2, [Cu(pepica)(pico)] (ClO4)2.(H2O), [Cu(dipica)(neoc)](ClO4)2.(H2O), [Cu(dipica)(bipy)](ClO4)2, [Cu(dipica)(phen)](ClO4)2, [Cu(dipica)(H2O)](ClO4)2, [Cu(dipica)(4ampy)](H2O)(ClO4)2, [Cu(dipica)(4phimH)](ClO4)2, [Cu(dipica)(4dmampy)](ClO4)2, [Cu(dipica)(nmim)](ClO4)2, [Cu(dipica)(2mimH)](ClO4)2, [Cu(dipica)(4mimH)](ClO4)2, [Cu(pepica)(4dmampy)](ClO4)2, [Cu(pepica)(3mpy)](ClO4)2, [Cu(pepica)(4mpy)](ClO4)2, [Cu(pepica)(imH)](ClO4)2, [Cu(pepica)(4mimH)](ClO4)2, [Cu(pepica)(4ampy)](ClO4)2, [Cu(dipica)Cl2], [Cu2(pepica)2Cl3]Cl, trans-fac-[Ni(dipica)2]Cl2.5H2O, trans-fac-[Ni(pepica)2]Cl2.5H2O, [VO2(bipy)](CF3SO3), and (C4H7N2)6V10O28.3H2O. These complexes have been characterized by elemental analyses, IR,UV-VIS and EPR spectroscopic measurements. X-ray crystal structures of the following complexes have been determined by using three-dimensional X-ray diffraction data. (1) cis-[Cu(dipica)2](ClO4)2, orthorhombic, space group F2dd, a  = 8.832(5) A, b = 22.129(5) A, c = 28.428(8) A, Z = 4, R = 0.036, Rw = 0.023. (2) trans-fac-and sq-py-[Cu(dipica)2](ClO4)2, Monoclinic, space group P21/n, a= 23.624(4) A, b = 9.369(4) A, c = 25.798(5) A, β = 95.60(2)°, Z = 4, R = 0.059, Rw = 0.061. (3) trans-fac-[Cu(pepica)2](ClO4)2, Orthorhombic, space group Pcab ,a = 12.028(4) A, b = 13.815(3) A, c = 17.701(5) A, Z = 4, R = 0.050. Rw= 0.038. (4) [Cu(pepica)(bipy)](ClO4)2, Monoclinic, space group P21/c, a  = 12.98(2) A, b = 8.89(1) A, c = 22.61(3) A, β = 96.19(1)° , Z = 4, R = 0.0732, Rw = 0.0859. (5) [Cu(dipica)(phen)](ClO4)2, Monoclinic, space group P21/ n, a = 13.627(4) A, b = 9.259 A (3), c = 21.926(4) A, β= 106.71(2)°, Z = 4, R = 0.0530, Rw = 0.1525. (6) [Cu(dipica)(nmim)](ClO4)2, Triclinic, space group P-1, a  8.4795(2), b = 8.6999(2), c = 16.4869(3) A; α = 78.821(1), β = 82.938(1), γ= 62.619(1), Z = 2, R = 0.0511, Rw =0.059. (7) [Cu(pepica)(4mpy)](ClO4)2, Triclinic, space group P-1, a  8.690(3), b = 8.808(3), c = 18.017(6) A; α= 76.65(3),β = 81.52(3),γ = 63.16(3), Z = 2, Rf = 0.080，Rw =0.087. (8) [Cu(pepica)(imH)](CH3CN)(ClO4)2, Monoclinic, space group P21/n a = 9.478(3), b = 8.205(2), c = 30.76(1) A; β = 93.11(3), Z = 4, R = 0.061，Rw =0.068 (9) [Cu(dipica)Cl2], Monoclinic, space group P21 / m, a =6.535(1) A, b = 13.375(3) A, c = 7.953(1) A, β = 103.38(1) , Z = 4, R = 0.028, Rw = 0.026. (10) [Cu2(pepica)2Cl3]Cl, Monoclinic, space group P21/ n, a  8.960(2) A, b = 13.008(3) A, c = 24.861(7) A,β = 91.210(2) , Z = 4, R = 0.029, Rw = 0.026. (11) [Ni(dipica)2]Cl2. 4H2O, Triclinic, space group P-1, a  8.756(2) A, b = 9.449(3) A, c = 9.542(3) A, α= 74.10(3) , β = 86.15(2) , γ= 80.52(2) , Z = 1, R = 0.046, Rw = 0.055. (12) [Ni(pepica)2]Cl2. 2H2O, Monoclinic, space group P21 / n, a  9.231(1) A, b = 9.016(1) A, c = 16.746(3) A, β = 104.01(1) , Z =2. R = 0.045, Rw = 0.037. (13) [V(O)2(bipy)2](CF3SO3), Monoclinic, space group P21 / n, a  15.433(2) A, b = 11.013(2) A, c = 27.423(2) A, β = 104.79(2) , Z = 4, R = 0.0697, Rw = 0.0821. (1) (C4H7N2)6V10O28.3H2O, Triclinic, space group P-1, a =  9.596(2) A，b = 11.487(3) A, c = 12.318(2) A, α= 93.77, β =102.73(2), γ=106.73(2) , Z = 1, R = 0.032, Rw = 0.029. Comparing the Gaussian component bands of the electronic spectra, the sequences of the d orbitals were assigned as dx2-y2 >> dz2 > dxy > dyz > dxz for solid and solution cis-[Cu(dipica)2](ClO4)2; dx2-y2 >> dxy > dz2 ~ dyz > dxz for solid trans-fac-[Cu(pepica)2](ClO4)2; dx2-y2 >> dxy > dyz ~ dz2 >  dxz for solution trans-fac-[Cu(pepica)2](ClO4)2; dx2-y2 >> dz2 > dxy > dyz ~ dxz for solution [Cu(pepica)(bipy)](ClO4)2, [Cu(pepica)(phen)](ClO4)2, [Cu(pepica)(neoc)](ClO4)2, [Cu(dipica)(neoc)](ClO4)2.(H2O), [Cu(dipica)(en)](ClO4)2 and [Cu(pepica)(pico)](ClO4)2.(H2O); dx2-y2 >> dz2 > dxy> dyz > dxz for solution [Cu(dipica)(bipy)](ClO4)2, and [Cu(dipica)(phen)](ClO4)2; dx2-y2 >> dxy > dyz > dxz > dz2 for solution [Cu(dipica)(L)](ClO4)2 and [Cu(pepica)(L)](ClO4)2.