NMR studies on the electronic structure of one-electron oxidized complexes of iron(III) porphyrinates

Akira Ikezaki, Yoshiki Ohgo, Mikio Nakamura

Research output: Contribution to journalArticle

39 Citations (Scopus)

Abstract

This review describes the relationship between the NMR chemical shifts and electronic structures of one-electron oxidized products of iron(III) porphyrins such as iron(III) porphyrin radical cations or iron(IV) porphyrins. In the case of the former complexes, the iron(III) ions are classified into four types; (i) high-spin (S = 5/2), (ii) mixed high- and intermediate-spin (S = 5/2, 3/2), (iii) low-spin with the (dxy)2(dxz, dyz)3 ground state, and (iv) low-spin with the (dxz, dyz)4(dxy)1 ground state. In the case of the latter complexes, they mostly have FeIV{double bond, long}O bonds. There is only one iron(IV) complex that has no FeIV{double bond, long}O bond. The complexes classified as above exhibit unique NMR chemical shifts. Thus, the NMR spectroscopy serves a quite useful tool to determine the fine electronic structures of the one-electron oxidized iron(III) porphyrin complexes.

Original languageEnglish
Pages (from-to)2056-2069
Number of pages14
JournalCoordination Chemistry Reviews
Volume253
Issue number15-16
DOIs
Publication statusPublished - 2009 Aug
Externally publishedYes

Fingerprint

Porphyrins
Electronic structure
Iron
Nuclear magnetic resonance
electronic structure
iron
porphyrins
nuclear magnetic resonance
Electrons
Chemical shift
Ground state
electrons
chemical equilibrium
Nuclear magnetic resonance spectroscopy
Cations
ground state
Ions
Positive ions
cations
products

Keywords

  • Iron(III)
  • Iron(IV)
  • NMR spectroscopy
  • One-electron oxidation
  • Porphyrin
  • Radical cation

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

NMR studies on the electronic structure of one-electron oxidized complexes of iron(III) porphyrinates. / Ikezaki, Akira; Ohgo, Yoshiki; Nakamura, Mikio.

In: Coordination Chemistry Reviews, Vol. 253, No. 15-16, 08.2009, p. 2056-2069.

Research output: Contribution to journalArticle

Ikezaki, Akira ; Ohgo, Yoshiki ; Nakamura, Mikio. / NMR studies on the electronic structure of one-electron oxidized complexes of iron(III) porphyrinates. In: Coordination Chemistry Reviews. 2009 ; Vol. 253, No. 15-16. pp. 2056-2069.
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