Dynamic Study of Metal-Ion Incorporation into Porphyrins Based on the Dynamic Characterization or Metal Ions and on Sitting-Atop Complex Formation

• FUNAHASHI Shigenobu

  Laboratory of Analytical Chemistry, Graduate School of Science, Nagoya University

• INADA Yasuhiro

  Research Center for Materials Science, Nagoya University

• INAMO Masahiko

  Department of Chemistry, Aichi University of Education

書誌事項

タイトル別名

• Dynamic Study of Metal-Ion Incorporation into Porphyrins Based on the Dynamic Characterization of Metal Ions and on Sitting-Atop Complex Formation

抄録

We succeeded in the detection of the sitting-atop (SAT) copper(II) complex of TPP (5,10,15,20-tetraphenylporphyrin) in acetonitrile (AN) as a solvent with a very low Brønsted basicity, where two pyrrolenine nitrogens in the Cu(II)-SAT complex coordinate to the metal ion and two protons still remain on the pyrrole nitrogens. The structure parameters around the copper(II) ion in the Cu(II)-SAT complex, as determined by a fluorescent EXAFS method, suggest an axially elongated and equatorially distorted six-coordinate geometry. We measured the rates of the formation reaction of the SAT complexes for a series of transition metal(II) ions in AN using the stopped-flow technique. We propose the mechanism where there is a rapid deformation equilibrium of the porphyrin ring prior to the rate-determining step of the bond rupture of a coordinated solvent molecule on the metal(II) ion. Furthermore, we measured the rates of the deprotonation reaction of the Cu(II)-SAT complex by some Brønsted bases and indicated that the rate-determining step is the attack of the base on the proton of the pyrrole nitrogen in the SAT complex. Finally, a unified mechanism relevant to the porphyrin metalation mechanism has been proposed.

収録刊行物

• Analytical Sciences

  Analytical Sciences 17 (8), 917-927, 2001

  社団法人 日本分析化学会

キーワード

• Analytical Chemistry

詳細情報

• CRID: 1390282679234089472
• NII論文ID: 10007177060
• NII書誌ID: AA10500785
• DOI: 10.2116/analsci.17.917
• COI: 1:CAS:528:DC%2BD3MXmt1Smsbo%3D
• ISSN: 13482246
• ISSN: 09106340
• NDL書誌ID: 5880762
• PubMed: 11708094
• Web Site: https://ndlsearch.ndl.go.jp/books/R000000004-I5880762
• Web Site: https://link.springer.com/content/pdf/10.2116/analsci.17.917.pdf
• Web Site: https://link.springer.com/article/10.2116/analsci.17.917/fulltext.html
• Web Site: https://www.jstage.jst.go.jp/article/analsci/17/8/17_8_917/_pdf
• 本文言語コード: en
• データソース種別:
  • JaLC
  • NDL
  • Crossref
  • PubMed
  • CiNii Articles
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