Methodology to determine the NMR chemical shifts of carbon atoms with radical character: A case of low-spin bis(tert-butylisocyanide) complex of (meso-tetrapropylporphyrinato)iron(III)

Yuka Niibori, Akira Ikezaki, Mikio Nakamura

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

Paramagnetic metal complexes sometimes exhibit no appreciable 13C NMR signals due to the short relaxation time. By making use of the fast self-exchange electron transfer between paramagnetic [Fe III(TPrP)(tBuNC)2]ClO4 and the corresponding diamagnetic [FeII(TPrP)(tBuNC)2], we have determined the chemical shifts of the carbon atoms that exhibit no signals due to the considerable amount of spin density. We have also determined the spin density of the meso carbon atom in [FeIII(TPrP)( tBuNC)2]ClO4 to be 0.076, which is to our knowledge the largest among all the low-spin iron(III) porphyrin complexes reported previously. This method is applicable to all the low-spin iron(III) porphyrinoids if the corresponding diamagnetic complexes are available.

Original languageEnglish
Pages (from-to)1469-1474
Number of pages6
JournalInorganic Chemistry Communications
Volume14
Issue number9
DOIs
Publication statusPublished - 2011 Sep

Fingerprint

Chemical shift
chemical equilibrium
Carbon
Iron
Nuclear magnetic resonance
methodology
iron
Atoms
nuclear magnetic resonance
carbon
Coordination Complexes
Porphyrins
Metal complexes
Relaxation time
atoms
Electrons
porphyrins
electron transfer
relaxation time
perchlorate

Keywords

  • C NMR
  • Electron configuration
  • Iron porphyrin
  • Self-exchange electron transfer
  • Spin density

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Methodology to determine the NMR chemical shifts of carbon atoms with radical character : A case of low-spin bis(tert-butylisocyanide) complex of (meso-tetrapropylporphyrinato)iron(III). / Niibori, Yuka; Ikezaki, Akira; Nakamura, Mikio.

In: Inorganic Chemistry Communications, Vol. 14, No. 9, 09.2011, p. 1469-1474.

Research output: Contribution to journalArticle

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AB - Paramagnetic metal complexes sometimes exhibit no appreciable 13C NMR signals due to the short relaxation time. By making use of the fast self-exchange electron transfer between paramagnetic [Fe III(TPrP)(tBuNC)2]ClO4 and the corresponding diamagnetic [FeII(TPrP)(tBuNC)2], we have determined the chemical shifts of the carbon atoms that exhibit no signals due to the considerable amount of spin density. We have also determined the spin density of the meso carbon atom in [FeIII(TPrP)( tBuNC)2]ClO4 to be 0.076, which is to our knowledge the largest among all the low-spin iron(III) porphyrin complexes reported previously. This method is applicable to all the low-spin iron(III) porphyrinoids if the corresponding diamagnetic complexes are available.

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