Enhancement of the Pfeiffer effect arising from the cation-cation interaction.
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概要
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The influence of added sodium and potassium chloride, bromide, and sulfate was examined on the Pfeiffer effect of the [Co(phen)<SUB>3</SUB>]<SUP>2+</SUP>- and [Ni(phen)<SUB>3</SUB>]<SUP>2+</SUP>-<I>d</I>-cinchoH<SUP>+</SUP> systems in water (phen=1,10-phenanthroline, and <I>d</I>-cinchoH<SUP>+</SUP>=<I>dextro</I>-cinchoninium ion). It was found that the added anions enhance the circular dichroism (CD) induced in the d-d transition region of [Co(phen)<SUB>3</SUB>]<SUP>2+</SUP> and [Ni(phen)<SUB>3</SUB>]<SUP>2+</SUP> ions, and that the CD-enhancing order is Br<SUP>−</SUP>>Cl<SUP>−</SUP>>SO<SUB>4</SUB><SUP>2−</SUP>/2. These findings were well interpreted in terms of reduced electrostatic repulsion between [Co(phen)<SUB>3</SUB>]<SUP>2+</SUP> or [Ni(phen)<SUB>3</SUB>]<SUP>2+</SUP> and <I>d</I>-cinchoH<SUP>+</SUP> by the added anions, and of the resulting enhanced enantiomerization of these cationic complexes in favor of <I>Δ</I>-isomers in the presence of <I>d</I>-cinchoH<SUP>+</SUP>. Logarithm of the magnitude of the induced CD was found to be a linear function of logarithm of the total anion concentration in all the systems examined. This fact gives a strong support to the above interpretation, and suggests a close resemblance of these Pfeiffer-active systems to aqueous cationic surfactant solutions.
- 公益社団法人 日本化学会の論文
著者
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YONEDA Hayami
Department of Chemistry, Faculty of Science, Hiroshima University
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Miyoshi Katsuhiko
Department Of Chemistry Faculty Of Science Hiroshima University
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Kuroda Yasushige
Department Of Chemistry Faculty Of Science Okayama University
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Okazaki Hiroshi
Department Of Bioscience Teikyo University Of Science And Technology
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Kuroda Yasushige
Department of Chemistry, Faculty of Science, Hiroshima University
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Okazaki Hiroshi
Department of Chemistry, Faculty of Science, Hiroshima University
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