A new series of copper(II) complexes derived from (4,5-dimethyl-3-pyrazolyl)aldazine (DMPA), formulated as: (a) [LCuX2]'nEtOH; (b) [LCu(H20)](C104)2; and (c) I-LCuX]BF4.nH20, where n = 1/2 or 1, X = C1 or Br and L = DMPA, have been synthesized. The formulations are based on elemental analyses and molar conductivity data. I.r., u.v.-vis., e.s.r, and magnetic data reveal that the complexes are trigonal bipyramidal, tetrahedral and stacked square-planar structures for (a), (b) and (c), respectively. The trigonal bipyramidal structure for class (a) compounds is confirmed using the atom superposition and electron delocalization-molecular orbital calculations, which agree with the experimental electronic spectral data. Variable temperature magnetic susceptibility data shows a ferromagnetic interaction within copper(II) complexes of class (c).
4,5-Dimethyl-3-pyrazolyl)aldazine, L, reacts with nickel(II) salts to form 1:1 and 1:2 complexes. The 1:1 binuclear systems involve two ligands bridging two nickels, in which L behaves as a tetradentate ligand, and the nickel(II) complexes have pseudo-octahedral stereochemistry. Some of the 1:1 and 1:2 complexes contain coordinated H20 and bridging OH. Structures of these complexes are proposed on the basis of elemental analyses, conductivity, spectral data (u.v.-vis. and i.r.) and magnetic susceptibilities.
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