Multidentate Ligand Substitution Reactions. XII. Substitution Reactions of the Nickel(II)-nitrilotriacetate Complex with Diethylenetriaminepentaacetic Acid in the Presence of Ethylenediamine and of the Nickel(II)-<I>N</I>-(2-hydroxyethyl)-iminodiacetate C
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概要
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The substitution reactions of the nickel(II)-nitrilotriacetate complex with diethylenetriaminepentaacetic acid in the presence of ethylenediamine and of the nickel(II)-<I>N</I>-(2-hydroxyethyl)-iminodiacetate complex with ethylenediaminetetraacetic acid and cyclohexane-1,2-diamine-<I>N</I>,<I>N</I>,<I>N</I>′,<I>N</I>′-tetraacetic acid were studied by employing the polarographic method. In the presence of ethylenediamine, the reaction of the nickel(II)-nitrilotriacetate complex with diethylenetriaminepentaacetic acid was found to proceed through the following four pathways:<BR>(<U>Remark: Graphics omitted.</U>)<BR>where X<SUP>3−</SUP> and Z<SUP>5−</SUP> denote completely-deprotonated nitrilotriacetate and diethylenetriaminepentaacetate anions respectively, and A<SUP>°</SUP>, ethylenediamine. By comparing the rate constants of the substitution reactions of the nickel(II)-nitrilotriacetate and ethylenediamine complexes with their dissociation rate constants, the structure of the reaction intermediate was determined. From the concentration dependence of the reaction rate, the reactions of the nickel(II)-<I>N</I>-(2-hydroxyethyl)-iminodiacetate complex with ethylenediaminetetraacetic acid and with cyclohexane-1,2-diamine-<I>N</I>,<I>N</I>,<I>N</I>′,<I>N</I>′-tetraacetic acid were concluded to proceed through the following two reaction pathways:<BR>(<U>Remark: Graphics omitted.</U>)<BR>where X<SUP>2−</SUP> and Y<SUP>4−</SUP> mean completely-deprotonated <I>N</I>-(2-hydroxyethyl)-iminodiacetate and ethylenediaminetetraacetate or cyclohexane-1,2-diamine-<I>N</I>,<I>N</I>,<I>N</I>′,<I>N</I>′-tetraacetate anions. From a comparison of the rate constants for the reaction of the <I>N</I>-(2-hydroxyethyl)-iminodiacetate complex with those for the corresponding reaction of the iminodiacetate complex, it was found that the hydroxyethyl group in the <I>N</I>-(2-hydroxyethyl)-iminodiacetate anion rather accelerates the dissociation of the <I>N</I>-(2-hydroxyethyl)-iminodiacetate anion from the nickel(II) ion.
- 公益社団法人 日本化学会の論文
著者
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Watanabe Toshiyuki
Department Of Agricultural Chemistry Faculty Of Agriculture Tohoku University
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Kodama Mutsuo
Department Of Chemistry College Of General Education Hirosaki University
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Karasawa Sadatsugu
Department of Chemistry, Ibaraki University
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