Effect of 2,2'-bipyridine on nickel (II)-halide interactions within their ternary complexes in N,N-dimethylformamide.
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概要
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The formation of ternary (2,2′-bipyridine)bromonickel(II) complexes has been studied by calorimetry in <I>N</I>,<I>N</I>-dimethylformamide containing 0.16 mol dm<SUP>−3</SUP> (C<SUB>2</SUB>H<SUB>5</SUB>)<SUB>4</SUB>-NClO<SUB>4</SUB> as a constant ionic medium at 25 °C. The data are well explained in terms of the formation of [NiBr(bpy)]<SUP>+</SUP> and [NiBr(bpy)<SUB>2</SUB>]<SUP>+</SUP> (bpy=2,2′-bipyridine), and their formation constants, enthalpies and entropies were determined. It is elucidated that the affinities of Br<SUP>−</SUP> as well as Cl<SUP>−</SUP> ions to [Ni(bpy)]<SUP>2+</SUP> and [Ni(bpy)<SUB>2</SUB>]<SUP>2+</SUP> are enhanced almost to the same extent over Ni<SUP>2+</SUP>. The enhancement is ascribed mainly to an increase in entropies upon complexation in both Ni<SUP>II</SUP>–Cl<SUP>−</SUP>–bpy and Ni<SUP>II</SUP>–Br<SUP>−</SUP>–bpy systems.
著者
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Ishiguro Shin-ichi
Department Of Chemistry Faculty Of Science Kyushu University
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Ozutsumi Kazuhiko
Department Of Applied Chemistry College Of Life Sciences Ritsumeikan University
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