Metalation of Water-Soluble Octabromoporphyrin with Lithium(I), Cadmium(II), and Mercury(II)

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著者

    • TABATA Masaaki
    • Department of Chemistry, Faculty of Science and Engineering, Saga University
    • NISHIMOTO Jun
    • Department of Chemistry, Faculty of Science and Engineering, Saga University
    • OGATA Akiko
    • Department of Chemistry, Faculty of Science and Engineering, Saga University
    • KUSANO Tohru
    • Department of Chemistry, Faculty of Science and Engineering, Saga University
    • NAHAR Nurun
    • Department of Chemistry, Faculty of Science and Engineering, Saga University

抄録

A water-soluble porphyrin, 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (H<sub>2</sub>obtpps<sup>4−</sup>; H<sub>2</sub>P<sup>4−</sup>) was synthesized and the equilibrium constants have been determined for the reaction of H<sub>2</sub>obtpps<sup>4−</sup> with lithium(I), cadmium(II), and mercury(II) at 25 °C in <i>I</i> = 0.1 mol dm<sup>−3</sup> (NaNO<sub>3</sub>). The protonation constants of H<sub>2</sub>obtpps<sup>4−</sup> were found to be 10<sup>4.83 ± 0.04</sup> mol<sup>−1</sup> dm<sup>3</sup>, 10<sup>1.96 ± 0.06</sup> mol<sup>−1</sup> dm<sup>3</sup>, and 10<sup>−10.02 ± 0.02</sup> mol dm<sup>−3</sup> for <i>K</i><sub>1</sub> = [H<sub>3</sub>P<sup>3−</sup>][H<sup>+</sup>]<sup>−1</sup>[H<sub>2</sub>P<sup>4−</sup>]<sup>−1</sup>, <i>K</i><sub>2</sub> = [H<sub>4</sub>P<sup>2−</sup>][H<sup>+</sup>]<sup>−1</sup>[H<sub>3</sub>P<sup>3−</sup>]<sup>−1</sup>, and <i>K</i><sub>−1</sub> = [HP<sup>5−</sup>][H<sup>+</sup>][H<sub>2</sub>P<sup>4−</sup>]<sup>−1</sup>, respectively. The porphyrin reacted with lithium(I) in alkaline aqueous solution to form LiP<sup>5−</sup>, of which formation constant was 10<sup>−18.81 ± 0.02</sup> mol dm<sup>−3</sup> for <i>K</i><sub>LiP</sub> = [LiP<sup>5−</sup>][H<sup>+</sup>]<sup>2</sup>[Li<sup>+</sup>]<sup>−1</sup>[H<sub>2</sub>P<sup>4−</sup>]<sup>−1</sup>. Sodium and potassium ions did not form their complexes under the same experimental conditions. The equilibrium constants for the formation of cadmium(II) and mercury(II) porphyrins defined by <i>K</i><sub>MP</sub> = [MP<sup>4−</sup>][H<sup>+</sup>]<sup>2</sup>[M<sup>2+</sup>]<sup>−1</sup>[H<sub>2</sub>P<sup>4−</sup>]<sup>−1</sup>, M = Cd<sup>2+</sup>; Hg<sup>2+</sup>, were 10<sup>−8.60 ± 0.13</sup> mol dm<sup>−3</sup> and 10<sup>0.12 ± 0.06</sup> mol dm<sup>−3</sup> for <i>K</i><sub>CdP</sub> and <i>K</i><sub>HgP</sub>, respectively. Mercury(II) also forms homodinuclear porphyrin, Hg<sub>2</sub>P, and the value was 10<sup>3.57 ± 0.03</sup> mol<sup>−1</sup> dm<sup>3</sup> for <i>K</i><sub>Hg<sub>2</sub>P</sub> = [Hg<sub>2</sub>P<sup>2−</sup>][Hg<sup>2+</sup>]<sup>−1</sup>[HgP<sup>4−</sup>]<sup>−1</sup>. The octabromo groups lower the basicity of the porphyrin, which results in the formation of lithium(I) porphyrin.

収録刊行物

  • Bulletin of the Chemical Society of Japan

    Bulletin of the Chemical Society of Japan 69(3), 673-677, 1996-03-15

    The Chemical Society of Japan

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各種コード

  • NII論文ID(NAID)
    10008900577
  • NII書誌ID(NCID)
    AA00580132
  • 本文言語コード
    ENG
  • 資料種別
    ART
  • ISSN
    00092673
  • データ提供元
    CJP書誌  CJP引用  J-STAGE 
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