Structure of Cobalt(II) Ion and Tri- and Tetrachlorocobaltate(II) Complexes in N,N-Dimethylformamide Determined by the Fluorescent EXAFS Method
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概要
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EXAFS (extended X-ray absorption fine structure) spectra were measured for <I>N</I>,<I>N</I>-dimethylformamide (DMF) solutions containing cobalt(II) ion and its chloro complexes of low concentration (20–40 mmol dm<SUP>−3</SUP>) by a laboratory EXAFS spectrometer modified for the fluorescence detection. The analysis of the EXAFS data for a cobalt(II) perchlorate DMF solution showed that cobalt(II) ion in DMF has an octahedral structure with six DMF molecules. The Co-O (DMF) bond length within [Co(dmf)<SUB>6</SUB>]<SUP>2+</SUP> in DMF is 206(1) pm and is practically the same as that within [Co(H<SUB>2</SUB>O)<SUB>6</SUB>]<SUP>2+</SUP> (208 pm) in water within experimental uncertainties. It was also shown that the tri- and tetrachlorocobaltate(II) complexes in DMF have a tetrahedral structure. The Co–O and Co–Cl lengths within [CoCl<SUB>3</SUB>(dmf)]<SUP>−</SUP> in DMF are 202(1) and 227(1) pm, respectively. The Co–Cl distances within [CoCl]<SUP>2−</SUP> in DMF and in water are the same and 229(1) pm.
著者
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Tohji Kazuyuki
Department Of Chemistry Faculty Of Science Gakushuin University
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Ishiguro Shin-ichi
Department Of Chemistry Faculty Of Science Kyushu University
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Ozutsumi Kazuhiko
Department Of Applied Chemistry College Of Life Sciences Ritsumeikan University
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Tohji Kazuyuki
Department of Molecular Structure, Institute for Molecular Science
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Udagawa Yasuo
Department of Molecular Structure, Institute for Molecular Science
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Ozutsumi Kazuhiko
Department of Chemistry, University of Tsukuba
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Udagawa Yasuo
Department of Chemistry, Faculty of Science, Tohoku University
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