Cobalt(III) Complexes with (N6-nXn)-Type Ligands. VII. Preparation and Properties of Isomers of the (Salicylamidato) cobalt(III) Complexes with Tris(2-aminoethyl)amine, Triethylenetetramine, and Ethylenediamine Ligands.

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概要

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• Title complexes of <I>t</I>- and <I>p</I>-[Co(<B>A</B>)(tren)]Cl<SUB>2</SUB>·H<SUB>2</SUB>O, <I>t</I>- and <I>p</I>-[Co(<B>C</B>)(tren)]Cl·H<SUB>2</SUB>O, <I>cis</I>-β<SUB>1</SUB> and β<SUB>2</SUB>-[Co(<B>A</B>)(trien)]Cl<SUB>2</SUB>·2H<SUB>2</SUB>O, <I>cis</I>-β<SUB>1</SUB>-[Co(<B>C</B>)(trien)]Cl·H<SUB>2</SUB>O, <I>cis</I>-β<SUB>1</SUB>-[Co(<B>D</B>)(trien)]Cl·H<SUB>2</SUB>O, [Co(<B>A</B>)(en)<SUB>2</SUB>]Cl<SUB>2</SUB>·H<SUB>2</SUB>O, [Co(<B>C</B>)(en)<SUB>2</SUB>]Cl·H<SUB>2</SUB>O, and [Co(<B>D</B>)(en)<SUB>2</SUB>]Cl·H<SUB>2</SUB>O have been obtained from a reaction mixture of [CoCl<SUB>2</SUB>L]Cl·H<SUB>2</SUB>O [L: tren, trien, or (en)<SUB>2</SUB>], Ag<SUB>2</SUB>O, and salicylamide.<BR>(<U>Remark: Graphics omitted.</U>)<BR>Separations of the <B>A</B>-, <B>C</B>-, and <B>D</B>-type complexes, and of the geometrical isomers of <I>t</I>- and <I>p</I>- or <I>cis</I>-β<SUB>1</SUB> and β<SUB>2</SUB> were attempted by using Dowex 50W-X2 column chromatography. Distinction of the <B>A</B>-, <B>C</B>-, and <B>D</B>-type complexes is described in the IR, <SUP>1</SUP>H, <SUP>13</SUP>C NMR, and absorption spectra; the solubility in DMSO; and the electric conductivities in aqueous solutions. The formation ratio of the <B>A</B>-, <B>C</B>-, and <B>D</B>-type complexes has been dependent upon the pH of the reaction mixture. The chemical shifts (δ=113–115) of the C-l carbon signals for the <B>A</B>-type complexes are at a higher field than those (δ=117–122) of the <B>C</B>- and <B>D</B>-type complexes. The ε values (3400–3700) of the charge transfer band at ca. 340 nm in the absorption spectra for the <B>A</B>-type complexes are greater than those (2500–3000) of the <B>C</B>- and <B>D</B>-type complexes. The <B>C</B>-type and <B>D</B>-type complexes are a linkage isomer. A characteristic property of the linkage isomer has been observed in the absorption and <SUP>13</SUP>C NMR spectra as well as the solubility in DMSO.

• 公益社団法人 日本化学会の論文

著者

• Yamamoto Yoshihisa

  Faculty Of Engineering Kyushu University

• Toyota Eiko

  Faculty of Pharmaceutical Science, Higashi Nippon Gakuen University

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