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Content available remote Direct synthesis as a new approach to heteropolynuclear complexes
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The idea of direct synthesis of coordination compounds - use of elemental metals or their oxides as starting materials - has been developed into "Salt route", "Ammonium salt route" and "Direct template synthesis", methods to synthesize heteropolynuclear complexes. The advantages of this approach in obtaining heterobi-, heterotrimetallic and mixed-anion heteropolynuclear coordination compounds are shown taking complexes of transition metals (Cu, Ni, Co, Mn, Zn, Cd) with aminoalcohols and ethylenediamine ligand as an example. The results of the X-ray crystal structure analysis and magnetic properties of the most interesting complexes are presented.
EN
Heteropolynuclear complexes of the type [M(diamine)2]3[Cr(NCS)6]2_nH2O, where diamine = N-methylethylenediamine (N-Me-en), 1,2-diaminopropane (pn); M = Ni(II), Cu(II) have been prepared by reacting [Cr(NCS)6]3- with the corresponding cationic [M(diamine)2]2+ complex in an aqueous solution. They have been characterized by elemental analysis, IR, UV-VIS, EPR, variable temperature magnetic susceptibility and thermal analysis. Spectroscopic studies reveal thiocyanato bridges between M(II)-Cr(III) centres. The parameters determined from temperature dependence on magnetic susceptibility (80-300 K) indicate moderate antiferromagnetic interactions for Ni(II)-Cr(III) and negligibly small or very weak ones for Cu(II)-Cr(III) systems. Magnetic studies suggest also presence of diamagnetic Ni(II) ions in the structure of Ni(II)-pn-Cr(III) complex. Thermal analysis shows higher thermal stability of Ni(II)-Cr(III) than Cu(II)-Cr(III) compounds. The process of thermal decomposition after dehydration is multistage and yields NiO + NiCr2O4and CuO + CuCrO2 as final products, respectively.
EN
New thiocyanato bridged complexes of the type [CuL4]3[Cr(NCS)6]2_mH2O [L = 1-methylimidazole (1-Meim), 2-methylimidazole (2-Meim), 1,2-dimethylimidazole (1,2- Me2im)] and [M(1-Meim)6]n[{M(1-Meim)4Cr(NCS)6}2n]_mH2O (M = Ni(II), Co(II) were prepared by the reaction of [Cr(NCS)6]3- with the appropriate [MLn]2+ complex in an aqueous solution and characterized by elemental and thermal analysis, IR, UV-VIS, EPR and temperature variable magnetic susceptibility. The presence of NCS bridges between M(II)-Cr(III) centres is evident from IR spectra. The electronic spectra correlate with proposal of different composition of Cu3Cr2 and M3Cr2(M = Ni, Co) systems. The parameters determined from temperature dependence on magnetic susceptibility (80-300 K) indicate weak or negligible antiferromagnetic interaction for obtained Cu(II)-Cr(III), Ni(II)-Cr(III) and Co(II)-Cr(III) systems. Thermal decomposition after dehydration is multistage and yields CuO + CuCrO2 and MIIO+MIICr2O4 as final products, respectively.
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