Four isomers of the bis(ethylenediamine)sarcosinatocobalt(III) ion: Separation, identification, and characterization.
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概要
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All four possible isomers of the bis(ethylenediamine)sarcosinatocobalt(III) ion, [Co(sar) (en)<SUB>2</SUB>]<SUP>2+</SUP>, were separated chromatographically on the column of an SP-Sephadex cation exchanger, and their absorption, circular dichroism, and <SUP>13</SUP>C NMR spectra were measured. The more stable pair of isomers were identified as <I>Δ</I>-[Co(<I>S</I>-sar) (en)<SUB>2</SUB>]<SUP>2+</SUP> and <I>Λ</I>-[Co(<I>R</I>-sar) (en)<SUB>2</SUB>]<SUP>2+</SUP>, while the less stable pair were <I>Δ</I>-[Co(<I>R</I>-sar) (en)<SUB>2</SUB>]<SUP>2+</SUP> and <I>Λ</I>-[Co(<I>S</I>-sar) (en)<SUB>2</SUB>]<SUP>2+</SUP>. The <I>Δ</I>-[Co(<I>S</I>-sar) (en)<SUB>2</SUB>]<SUP>2+</SUP> isomer in an aqueous solution showed mutarotation which can be ascribed to a change in configuration (epimerization) about the sarcosinato nitrogen atom. In equiribrium at 25°C, the mixture consisted of 84.8% of the <I>Δ</I>(<I>S</I>) isomer and 15.2% of the <I>Δ</I>(<I>R</I>) isomer. From this result, the free-energy difference between the isomers was estimated to be 4.2<SUB>6</SUB> kJ mol<SUP>−1</SUP>. The presence of the less stable isomers, which were not found by Buckingham <I>et al.</I>, was also confirmed by the <SUP>13</SUP>C NMR measurements.
- 公益社団法人 日本化学会の論文
著者
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Yoshikawa Yuzo
Department Of Chemistry Faculty Of Science Okayama University
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Yamatera Hideo
Department of Chemistry, Faculty of Science, Nagoya University
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Fujita Miho
Department of Chemistry, Faculty of Science, Nagoya University
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