Preparation of polyoxa-1,n-dithia(n)(1,1')ruthenocenophanes and the structural studies of their metal complexes.

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概要

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• Polyoxa-1,<I>n</I>-dithia[<I>n</I>](1,1′)ruthenocenophanes were prepared by treatment of 1,1′-ruthenocenedithiol with α, ω-dibromo polyethers. The ruthenocenophanes formed efficiently complexes with soft ions, but not with hard and borderline cations. The <SUP>1</SUP>H- and <SUP>13</SUP>C-NMR spectral data of the silver(I) ion-complexed ruthenocenophanes suggested a partial electron-transfer interaction between the ruthenium atom of the ruthenocene nucleus and the incapsulated silver(I) ion. The crystal structure of the 1:1 complex of 4,7,10,13-tetraoxa-1,16-dithia[16](1,1′)ruthenocenophane with mercury(II) chloride was determined by the X-ray method. The crystals are triclinic, space group P\bar1, with <I>a</I>=13.722(3), <I>b</I>=11.678(4), <I>c</I>=8.179(2) Å, α=102.69(3), β=72.82(2), γ=100.73(2)°, <I>Z</I>=2, <I>D</I><SUB>x</SUB>=2.11 g cm<SUP>−3</SUP>. The mercury(II) cation and the two chloride ions are situated in the central cavity of the macrocyclic moiety and at the apexes, respectively. The distance between the ruthenium atom of a ruthenocene nucleus and the incapsulated mercury(II) ion is 4.846 (2) Å which is too long for direct metal–metal interaction.

• 公益社団法人 日本化学会の論文

著者

• SATO Masaru

  Chemical Analysis Center, Saitama University

• Akabori Sadatoshi

  Department Of Chemistry Faculty Of Science Toho University

• Sato Sadao

  Analytical And Metabolic Research Laboratories Sankyo Co. Ltd.

• Sato Masaru

  Chemical Analysis Center Saitama University

• Kawazoe Kayoko

  Analytical and Metabolic Research Laboratories, Sankyo Co. Ltd.

• Tamura Chihiro

  Analytical and Metabolic Research Laboratories, Sankyo Co. Ltd.

• Tamura Chihiro

  Analytical and Metabolic Research Laboratories, Sankyo Co., Ltd.

• Habata Yoichi

  Department of Chemistry, Faculty of Science, Toho University

• Munegumi Hiroyuki

  Department of Chemistry, Faculty of Science, Toho University

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