Ionic association ofmixed nickel (II) chelates in alcohols, ketones, and nitrobenzene.
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概要
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The conductances of mixed nickel(II) chelates, [Ni(acac)(<I>N</I>,<I>N</I>,<I>N</I>′,<I>N</I>′-tmen)]X (where acac=2,4-pentanedionato, <I>N</I>,<I>N</I>,<I>N</I>′,<I>N</I>′-tmen=<I>N</I>,<I>N</I>,<I>N</I>′,<I>N</I>′-tetramethylethylenediamine, and X<SUP>−</SUP>=ClO<SUB>4</SUB><SUP>−</SUP> or NO<SUB>3</SUB><SUP>−</SUP>), in alcohols {ethanol (EtOH), 1-propanol (<I>n</I>-PrOH), 2-propanol (<I>i</I>-PrOH), and 1-butanol (<I>n</I>-BuOH)}, ketones {acetone (Me<SUB>2</SUB>CO), methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK)}, and nitrobenzene (PhNO<SUB>2</SUB>) were measured at 25 °C. The obtained ionic association constants (<I>K</I><SUB>a</SUB>) of [Ni(acac)(<I>N</I>,<I>N</I>,<I>N</I>′,<I>N</I>′-tmen)]ClO<SUB>4</SUB> which were derived by using the extended Fouss–Hsia function indicated that (1) the perchlorate complex is a normal type of uni-uni-valent electrolyte and (2) it is more dissociated than [Co(acac)<SUB>2</SUB>(<I>N</I>,<I>N</I>,<I>N</I>′,<I>N</I>′-tmen)]ClO<SUB>4</SUB> in EtOH, <I>n</I>-PrOH, and <I>n</I>-BuOH. Walden products of the cations suggest that the nickel(II) chelate cation in the alcohols is present as an octahedral form with the coordination of two solvent molecules. On the other hand, <I>K</I><SUB>a</SUB> of [Ni(acac)(<I>N</I>,<I>N</I>,<I>N</I>′,<I>N</I>′-tmen)]NO<SUB>3</SUB> are much larger than those of [Ni(acac)(<I>N</I>,<I>N</I>,<I>N</I>′,<I>N</I>′-tmen)]ClO<SUB>4</SUB>. This can be ascribed to the coordination of a nitrate ion to the nickel(II) ion. The effect is large and approximately the same in the ketones and PhNO<SUB>2</SUB>, though small in EtOH, <I>n</I>-PrOH, and <I>n</I>-BuOH due to the coordination of solvent molecules.
- 公益社団法人 日本化学会の論文
著者
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Ito Kazuaki
Department Of Applied Chemistry Nagoya Institute Of Technology
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Yamamoto Yuroku
Environmental and Safety Engineering Department, Fukui Institute of Technology
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