The photochemical formation of the .PI.-cation radical from chloro(5,10,15,20-tetraphenylporphyrinato)cobalt(III) in aerated dichloromethane.

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概要

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• Chloro(5,10,15,20-tetraphenylporphyrinato)cobalt(III), Co<SUP>III</SUP>(tpp)Cl, in an aerated dichloromethane(DCM) solution undergoes photooxidation to produce the porphyrin π-cation radicals, Co<SUP>III</SUP>(tpp)<SUP>+·</SUP>Cl<SUB>2</SUB>. The formation mechanism of the π-cation radical was investigated by means of optical absorption and ESR spectroscopy: Co<SUP>III</SUP>(tpp)Cl in DCM decomposes photochemically to yield Co<SUP>II</SUP>(tpp) and chlorine atoms, which then abstract hydrogen atoms from DCM molecules to yield solvent radicals, ·CHCl<SUB>2</SUB>, and HCl. The solvent radicals react with oxygen molecules, resulting in the generation of peroxyl radicals, which then oxidize Co<SUP>III</SUP>(tpp)Cl to produce the π-cation radicals, Co<SUP>III</SUP>(tpp)<SUP>+·</SUP>Cl<SUB>2</SUB>.

• 公益社団法人 日本化学会の論文

著者

• Hoshino Mikio

  The Institute Of Physical And Chemical Research

• Kohno Masahiro

  JEOL Ltd.

• Yamamoto Kiyoko

  The Institute of Physical and Chemical Research

• Yamamoto Kiyoko

  The Institute of Physical and Chemical Research(RIKEN)

• Ohya-Nishiguchi Hiroaki

  Department of Chemistry, Faculty of Science, Kyoto University

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