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 journalReview article

41 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

Keywords

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

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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