Formation and characterization of five- and six-coordinate iron(III) corrolazine complexes

Satoshi Kurahashi, Takahisa Ikeue, Tamotsu Sugimori, Masashi Takahashi, Masahiro Mikuriya, Makoto Handa, Akira Ikezaki, Mikio Nakamura

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6 Citations (Scopus)

Abstract

Electronic structures of five- and six-coordinate iron(III) corrolazine complexes are determined by means of 1H NMR, 13C NMR, EPR, and Mössbauer spectroscopy as well as SQUID magnetometry. A series of five-coordinate complexes, [FeIII(TBP8Cz)(L)]* where the axial ligands(L) are cyanide(CN-), imidazole(HIm), 1-methylimidazole(1-MeIm), 4-(N,N-dimethylamino)pyridine(DMAP), pyridine(Py), 4-cyanopyridine(4-CNPy), and tert-butylisocyanide(tBuNC), are obtained by the addition of 1 to 2 equiv. of the ligands to the dichloromethane solutions of FeIII(TBP8Cz) at 298 K: TBP8Cz is a trianion of 2,3,7,8,12,13,17,18-octakis(4-tert-butylphenyl)corrolazine. These complexes commonly show the S = 3/2 at 298 K. By contrast, formation of the six-coordinate complexes depends on the nature of the axial ligands. While the addition of 3 equiv. of CN- has completely converted Fe III(TBP8Cz) to (Bu4N)2[Fe III(TBP8Cz)(CN)2] at 298 K, the conversion to the bis-adduct is only attained below ca. 200 K in the case of HIm, 1-MeIm, and DMAP even in the presence of 50 equiv. of the ligands. If the axial ligand is Py, 4-CNPy, or tBuNC, the formation of [FeIII(TBP 8Cz)(L)2] is confirmed only at an extremely low temperature (15 K). Close inspection of the 1H NMR and EPR spectra has revealed that all the bis-adducts adopt the (dxy) 2(dxz, dyz)3 ground state. While FeIII(TBP8Cz) forms paramagnetic bis- and mono-adduct in toluene solution at 298 K in the presence of excess amount of CN- and tBuNC, respectively, the corresponding porphyrazine complex, [FeIII(TBP8Pz)]Cl, forms diamagnetic bis-CN and bis- tBuNC under the same conditions: TBP8Pz is a dianion of 2,3,7,8,12,13,17,18-octakis(4-tert-butylphenyl)-porphyrazine. Thus, the iron(III) ion of porphyrazine complex is more easily reduced than that of the corresponding corrolazine complex.

Original languageEnglish
Pages (from-to)518-529
Number of pages12
JournalJournal of Porphyrins and Phthalocyanines
Volume16
Issue number5-6
DOIs
Publication statusPublished - 2012

Keywords

  • corrolazine
  • electron configuration
  • iron(III) complexes
  • spin state

ASJC Scopus subject areas

  • Chemistry(all)

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