One-electron oxidized product of difluoroiron(iii) porphyrin: Is it iron(iv) porphyrin or iron(iii) porphyrin π-cation radical?

Akira Ikezaki, Masashi Takahashi, Mikio Nakamura

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The electronic structure of [Fe(TMP)F 2], which is formally a one-electron oxidation equivalent above [Fe III(TMP)F 2] -, has been examined in solution by 1H NMR, UV-Vis, and Mössbauer spectroscopy. In CD 2Cl 2-CD 3OD solution at 193 K, the pyrrole-H and m-H signals appeared at 128.2 and 116.7 ppm, respectively. The UV-Vis spectrum showed broad absorption bands at 560-680 nm. The Mössbauer spectrum taken in frozen toluene-methanol solution exhibited a very broad single line from which the IS and QS values were determined by computer simulation to be 0.50 and 0.14 mm s -1, respectively. On the basis of these results, it was concluded that the one-electron oxidized product of [Fe(TMP)F 2] - should be formulated as the iron(iii) radical cation [Fe III(TMP) F 2], not as iron(iv) porphyrin [Fe IV(TMP)F 2] as previously suggested.

Original languageEnglish
Pages (from-to)9163-9168
Number of pages6
JournalDalton Transactions
Issue number36
Publication statusPublished - 2011 Sep 28


ASJC Scopus subject areas

  • Inorganic Chemistry

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