Cobalt(III) complexes with quadridentate ligands. VIII. The preparation and properties of cis-.BETA.1 and .BETA.2-isomers of the thiosalicylato(quadridentate amine)cobalt(III) complexes.

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概要

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• <I>cis</I>-β<SUB>1</SUB> and β<SUB>2</SUB>-Thiosalicylato(quadridentate amine)cobalt(III) complexes, <I>cis</I>-β<SUB>1</SUB>, β<SUB>2</SUB>-[Co(thiosal)L]X·<I>n</I>H<SUB>2</SUB>O (L: trien (2,2,2-tet), 3,2,3-tet; X: Cl, NO<SUB>3</SUB>), have been prepared from a reaction mixture of [CoCl<SUB>2</SUB>L]Cl·<I>n</I>H<SUB>2</SUB>O (L: trien, 3,2,3-tet), Ag<SUB>2</SUB>O, thiosalicylic acid (<I>o</I>-mercaptobenzoic acid), and 28% aqueous ammonia. Two geometrical isomers (cis-β<SUB>1</SUB> and β<SUB>2</SUB>) of their complexes were separated by Dowex 50W-X2 column chromatography. The isomerization between the cis-β<SUB>1</SUB> and β<SUB>2</SUB>-isomers is reversible in water at 40 °C. The IR spectra of these complexes showed four or five absorption bands in the 990–1100 cm<SUP>−1</SUP> region and four absorption bands in the 3000–3300 cm<SUP>−1</SUP> region. This indicates that these complexes assume the cis-β<SUB>1</SUB>-form. Their cis-β<SUB>1</SUB> and β<SUB>2</SUB> configurations have been established by their absorption and NMR spectra. The cis-β<SUB>1</SUB> and β<SUB>2</SUB>-thiosalicylato(trien)cobalt(III) complexes have been tentatively assigned to the <I>RR</I>,<I>SS</I> diastereoisomer by their <SUP>1</SUP>H NMR spectra. The color of solid state materials, solubilities in alcohols, isomerization at 40 °C, reaction in 60% nitric acid, absorption spectra, and chemical shift of Co–S–C carbon of the coordinated thiosalicylato ligand for the title complexes are different from those of the corresponding <I>cis</I>-β<SUB>1</SUB> and β<SUB>2</SUB>-salicylato(quadridentate amine)cobalt(III) complexes, <I>cis</I>-β<SUB>1</SUB>, β<SUB>1</SUB>-[Co(sal)L]Cl·<I>n</I>H<SUB>2</SUB>O (L: trien, 2,3,2-tet, 3,2,3-tet, 3,3,3-tet), reported previously.

• 公益社団法人 日本化学会の論文

著者

• Yamamoto Yoshihisa

  Faculty Of Engineering Kyushu University

• Yoshii Kayoko

  Faculty of Pharmaceutical Sciences, Higashi Nippon Gakuen University

• Toyota Eiko

  Faculty of Pharmaceutical Science, Higashi Nippon Gakuen University

• Konno Kazuko

  Faculty of Pharmaceutical Sciences, Higashi Nippon Gakuen University

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