Relative acidity of bis(2,4-pentanedionato)(diamine)cobalt(III) complexes in lower dielectric solvents.
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概要
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The conductances of bis(2,4-pentanedionato)(diamine)cobalt(III) complexes ([Co(acac)<SUB>2</SUB>(diamine)]X, diamine: ethylenediamine (en) and <I>N</I>,<I>N</I>′-dimethylethylenediamine (<I>N</I>,<I>N</I>′-dmen), X=Br<SUP>−</SUP> and ClO<SUB>4</SUB><SUP>−</SUP>) were measured in aprotic solvents covering the approximate range of dielectric constant 5–28 at 25 °C. It was found that a) in spite of the larger size of the methyl derivative the ionic association constants (<I>K</I><SUB>a</SUB>) for [Co(acac)<SUB>2</SUB>(<I>N</I>,<I>N</I>′-dmen)]<SUP>+</SUP> complexes are larger than those for [Co(acac)<SUB>2</SUB>(en)]<SUP>+</SUP> complexes in all the composition of nitrobenzene (PhNO<SUB>2</SUB>) carbon tetrachloride (CCl<SUB>4</SUB>) mixtures (wt % CCl<SUB>4</SUB>: 20, 40, 60, 70). b) The reverse trend was obtained in dichloromethane (DCM), 1,1,2,2-tetrachloroethane (1,1,2,2-TCE), and chloroform (CHCl<SUB>3</SUB>). These results were explained in terms of hydrogen bonding between the NH protons in the chelate cations and the anions ClO<SUB>4</SUB><SUP>−</SUP> and Br<SUP>−</SUP>, selective solvation of the NH group side by nitrobenzene, and the desolvation due to the introduction of the <I>N</I>-methyl groups. The relative acidity of NH protons which is controlled by solvation plays an important role in ionic association for the chelate cations with NH protons.
- 公益社団法人 日本化学会の論文
著者
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Yamamoto Yuroku
Department Of Chemistry Faculty Of Science Hiroshima University
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Ito Kazuaki
Department Of Applied Chemistry Nagoya Institute Of Technology
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Yamamoto Manabu
Department of Applied Electronics, Tokyo University of Science, 2641 Yamasaki, Noda, Chiba 278-8510, Japan
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Hasegawa Kazuko
Department of Chemistry, Faculty of Science, Hiroshima University
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Iwamoto Etsuro
Department of Chemistry, Faculty of Science, Hiroshima University
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