Structure and racemization of optically active mer-(3-azapentane-1,5-diamine or 3-methyl-3-azapentane-1,5-diamine)(ethylenediamine-N-acetato)cobalt(III) complexes.
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概要
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The crystal structure of (−)<SUB>500</SUB><SUP>CD</SUP>-<I>mer</I>-[Co(edma)(dien)]Br<SUB>2</SUB>·2/3CH<SUB>3</SUB>OH·2/3H<SUB>2</SUB>O was determined by the X-ray diffraction method. The crystal is triclinic, space group <I>P</I>1, <I>a</I>=13.824(8), <I>b</I>=13.814(8), <I>c</I>=8.055(3) Å, α=101.18(6), β=101.17(6), γ=116.32(5)°, and <I>Z</I>=3. All of the crystallographically independent complex cations, in which the terdentate ligands coordinate meridionally, have a δ spiral configuration, and the asymmetric nitrogen donor atoms of the edma ligands take an <I>S</I> configuration. The racemization reactions due to the inversion at the secondary amine nitrogen atom of the edma ligand in (−)<SUB>500</SUB><SUP>CD</SUP>-<I>mer</I>-[Co(edma)(dien)]<SUP>2+</SUP> and (−)<SUB>514</SUB><SUP>CD</SUP>-<I>mer</I>-[Co(edma)(mdien)]<SUP>2+</SUP> were studied at 20–35 °C in the pH range of 6.10–7.24. The rate law for both complexes was described as <I>R</I>=<I>k</I>[OH<SUP>−</SUP>][complex]. The activation parameters at 30.0 °C were Δ<I>H</I><SUP>\neweq</SUP> of 94.9 kJ mol<SUP>−1</SUP> and Δ<I>S</I><SUP>\neweq</SUP> of 126 J K<SUP>−1</SUP> mol<SUP>−1</SUP> for the dien complex and Δ<I>H</I><SUP>\neweq</SUP> of 73.8 kJ mol<SUP>−1</SUP> and Δ<I>S</I><SUP>\neweq</SUP> of 62.0 J K<SUP>−1</SUP> mol<SUP>−1</SUP> for the mdien complex.
- 公益社団法人 日本化学会の論文
著者
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Yasui Takaji
Department Of Chemistry Faculty Of Science Kochi University
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Ama Tomoharu
Department Of Chemistry Faculty Of Science Kochi University
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Okamoto Ken-ichi
Department Of Advanced Materials Science & Engineering Faculty Of Engineering Yamaguchi Universi
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Kawaguchi Hiroshi
Department Of Applied Chemistry Faculty Of Engineering Utsunomiya University
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Hidaka Jinsai
Department of Chemistry Faculty of Science Osaka University
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Fukaki Hironobu
Department of Chemistry, Faculty of Science, Kochi University
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