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

doi:10.1039/c1dt10561b

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

Department of Radiology

Research output: Contribution to journal › Article › peer-review

11 Citations (Scopus)

Abstract

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 language	English
Pages (from-to)	9163-9168
Number of pages	6
Journal	Dalton Transactions
Volume	40
Issue number	36
DOIs	https://doi.org/10.1039/c1dt10561b
Publication status	Published - 2011 Sept 28

ASJC Scopus subject areas

Inorganic Chemistry

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

abstract = "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 M{\"o}ssbauer 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 M{\"o}ssbauer 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.",

author = "Akira Ikezaki and Masashi Takahashi and Mikio Nakamura",

year = "2011",

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doi = "10.1039/c1dt10561b",

language = "English",

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T1 - One-electron oxidized product of difluoroiron(iii) porphyrin

T2 - Is it iron(iv) porphyrin or iron(iii) porphyrin π-cation radical?

AU - Ikezaki, Akira

AU - Takahashi, Masashi

AU - Nakamura, Mikio

PY - 2011/9/28

Y1 - 2011/9/28

N2 - 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.

AB - 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.

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

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