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

Research output: Contribution to journalArticle

10 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 languageEnglish
Pages (from-to)9163-9168
Number of pages6
JournalDalton Transactions
Volume40
Issue number36
DOIs
Publication statusPublished - 2011 Sep 28

Fingerprint

Thymidine Monophosphate
Porphyrins
Cations
Iron
Electrons
Pyrroles
Toluene
Electronic structure
Methanol
Absorption spectra
Nuclear magnetic resonance
Spectroscopy
Oxidation
Computer simulation

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

One-electron oxidized product of difluoroiron(iii) porphyrin : Is it iron(iv) porphyrin or iron(iii) porphyrin π-cation radical? / Ikezaki, Akira; Takahashi, Masashi; Nakamura, Mikio.

In: Dalton Transactions, Vol. 40, No. 36, 28.09.2011, p. 9163-9168.

Research output: Contribution to journalArticle

Ikezaki, Akira ; Takahashi, Masashi ; Nakamura, Mikio. / One-electron oxidized product of difluoroiron(iii) porphyrin : Is it iron(iv) porphyrin or iron(iii) porphyrin π-cation radical?. In: Dalton Transactions. 2011 ; Vol. 40, No. 36. pp. 9163-9168.
@article{fd905e8c42954958a1bb3f7a8c55c2f9,
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",
month = "9",
day = "28",
doi = "10.1039/c1dt10561b",
language = "English",
volume = "40",
pages = "9163--9168",
journal = "Dalton Transactions",
issn = "1477-9226",
publisher = "Royal Society of Chemistry",
number = "36",

}

TY - JOUR

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.

UR - http://www.scopus.com/inward/record.url?scp=80052536217&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=80052536217&partnerID=8YFLogxK

U2 - 10.1039/c1dt10561b

DO - 10.1039/c1dt10561b

M3 - Article

C2 - 21826314

AN - SCOPUS:80052536217

VL - 40

SP - 9163

EP - 9168

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

IS - 36

ER -