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By [[author]]余俊益 and 余俊益


[[abstract]]Mixed-ligand N-salicylidenealaninato, N-salicylidenephenylalaninato and N-(2-hydroxybenzyl)phenylalaninato copper(Ⅱ) complexes, Cu(sal-L- ala)(L), Cu(sal-L-phe)(L) and Cu(salh-L-phe)(L), have been synthesized, where L=4-methylpyridine (4mpy), 4-aminopyridine (4apy). 4- dimethylaminopyridine (dmap), imidazole (imH), 4-methyl-imidazole (4mimH), 2-methylimidazole (2mimH), 4-phenyl-imidazole (4phimH) or neocuproine (neoc). These complexes have been characterized by elemental analysis, UV-vis, CD, IR, and EPR spectroscopic measurements. By using three-dimensional X-ray diffraction methods, the crystal and molecular structures of the following six complexes have been determined. The crystal data of these complexes are given below: (1) Cu(sal-L-ala)(imH) monoclinic, space group P21, with a=7.9862(6)A, b=9.9257(7)A, c=17.4768(7)A; β=100.256(1)°, V=1363.2(5)A3, Z =4, R=0.0386 and Rw=0.0364. (2) Cu(sal-L-ala)(neoc) monoclinic, space group C2/c, with a=28.012(18)A, b=12.205(3)A, c=12.535(3)A ;β =92.04(4)°,V=4283(3)A3, Z=8, R=0.089 and Rw=0.082. (3) Cu(sal-L-phe)(dmap) monoclinic, space group P21, with a=10.6440(19)A, b=8.7584(9)A, c=11.0929(15)A ,β =97.213(15)°, V=1025.9(3)A3, Z=2, R=0.028 and Rw=0.030. (4) Cu(sal-D-phe)(dmap) monoclinic, space group P21, witha=10.6490(6)A, b=8.7685(5)A, c=11.0975(15)A ;β= 97.160(1)°, V=1028.2(4)A3, Z=2, R=0.0358 and Rw=0.0345. (5) Cu(sal-L-phe)(4apy) triclinic, space group P1, with a=8.3643(6)A, b=10.2286(7)A, c=11.0618(7)A α=95.169(0)°, β=98.869(1)°, γ=95.087(1)°, V=4283(3)A3, Z=2, R=0.0342 and Rw=0.0344. (6) Cu(sal-L-phe)(neoc) orthorhombic, space group P212121, with a=9.4665(6)A, b=10.2210(7)A, c=25.5289(17)A; V=2470.1(7) A3 Z=4, R=0.0402 and Rw=0.0309. Based on the X-ray structures, EPR, UV-vis and CD spectral data, the molecular structures of Cu(sal-L-ala)(L) and Cu(sal-L-phe)(L) complexes are square pyramidal, deduced from Gaussian analyses of the visible and CD spectra. The sequences of the d orbitals are assigned as:dx2-y2>>dz2>dyz>dxy>dxz There are two exceptions. The molecular structure of Cu(sal-L- ala)(4apy) and Cu(sal-L-ala)(4phimH), by visible spectral Gaussian analysis, are square planar. Their sequence of d orbitals is assigned as: dx2-y2>>dyz>dxy>dxz>dz2 In the Cu(salh-L-phe)(L) series, by EPR, UV-vis, CD spectrum and Gaussian analysis, their structure are square planar in liquid state but square pyramidal in solid state. The sequences of d orbitals are assigned as: liquid state: dx2-y2>>dxy>dyz>dxz>dz2 solid state: dx2-y2>>dz2>dxy>>dyz>dxz

Topics: 柳亞丙胺酸, 柳亞苯丙胺酸, [[classification]]39
Year: 2010
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