Electron configuration of ferric ions in low-spin (dicyano)(meso-tetraarylporphyrinato)iron(III) complexes

Mikio Nakamura, Takahisa Ikeue, Akira Ikezaki, Yoshiki Ohgo, Hiroshi Fujii

Research output: Contribution to journalArticle

28 Citations (Scopus)

Abstract

The electron configuration of a series of low-spin (dicyano){meso-tetrakis(2,4,6-trialkylphenyl)porphyrinato}iron(III) complexes, [Fe(R-TPP)(CN)2]- where R = Me, Et, or iPr, together with the parent [Fe(TPP)(CN)2]-, has been examined in dichloromethane-methanol solution by 1H NMR, 13C NMR, and EPR spectroscopies. While the ferric ion of [Fe(TPP)(CN)2]- has shown a common (dxy)2(dxzdyz)3 configuration, the ferric ions of the alkyl-substituted complexes [Fe(R-TPP)(CN)2]- have exhibited the preference of a less common (dxz,dyz)4(dxy)1 configuration. Spectroscopic characteristics of the complexes in which ferric ions take the (dxz,dyz)4(dxy)1 configuration are (i) axial type EPR spectra, (ii) downfield shifted pyrrole and meta signals in 1H NMR spectra, and (iii) downfield shifted meso-caibon signals in 13C NMR spectra. Occurrence of the less common (dxz,dyz)4(dxy)1 configuration in [Fe(R-TPP)(CN)2]- has been ascribed to the electronic interaction between iron(dπ) and cyanide(pπ*) orbitals. The interaction stabilizes the dπ orbitals and induces (dxzdyz)4(dxy)1 configuration. Since the electron configuration of (dicyano){meso-tetrakis(2,6-dichlorophenyI)porphyrinato}iron(III), [Fe(Cl-TPP)(CN)2]-, which carries bulky electronegative chlorine atoms at the ortho positions, is presented as a common (dxy)2(dxzdyz)3, the less common (dxz,dyz)4(dxy)1 configuration in [Fe(R-TPP)(CN)2]- can be ascribed, at least partially, to the electron-donating ability of the meso-aryl groups.

Original languageEnglish
Pages (from-to)3857-3862
Number of pages6
JournalInorganic Chemistry
Volume38
Issue number17
DOIs
Publication statusPublished - 1999

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Fingerprint Dive into the research topics of 'Electron configuration of ferric ions in low-spin (dicyano)(meso-tetraarylporphyrinato)iron(III) complexes'. Together they form a unique fingerprint.

  • Cite this