Electronic Structures of Active Site Models for Compounds I and II of Peroxidase

Stephen F. Sontum, David Case

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

Xα multiple scattering calculations are reported for the d4 oxo complexes Fe(P)(py)(O)0, 1+(P = porphine, py = pyridine), models for the active sites of intermediates I and II of horseradish peroxidase. Orbital energy trends for the addition of pyridine and then oxygen to Fe(II) porphine are used to rationalize spin and oxidation states of these clusters. Particular attention is paid to comparisons with ENDOR spectral data on intermediate I. Our results suggest that both a and ir spin transfer to the ligands is important and that the spins localized at the FeO and porphyrin sites interact strongly.

Original languageEnglish (US)
Pages (from-to)4013-4015
Number of pages3
JournalJournal of the American Chemical Society
Volume107
Issue number13
DOIs
StatePublished - Jan 1 1985
Externally publishedYes

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Pyridine
Peroxidase
Electronic structure
Catalytic Domain
Multiple scattering
Porphyrins
Electron Spin Resonance Spectroscopy
Horseradish Peroxidase
Ligands
Oxygen
Oxidation
porphine
pyridine

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

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abstract = "Xα multiple scattering calculations are reported for the d4 oxo complexes Fe(P)(py)(O)0, 1+(P = porphine, py = pyridine), models for the active sites of intermediates I and II of horseradish peroxidase. Orbital energy trends for the addition of pyridine and then oxygen to Fe(II) porphine are used to rationalize spin and oxidation states of these clusters. Particular attention is paid to comparisons with ENDOR spectral data on intermediate I. Our results suggest that both a and ir spin transfer to the ligands is important and that the spins localized at the FeO and porphyrin sites interact strongly.",
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Electronic Structures of Active Site Models for Compounds I and II of Peroxidase. / Sontum, Stephen F.; Case, David.

In: Journal of the American Chemical Society, Vol. 107, No. 13, 01.01.1985, p. 4013-4015.

Research output: Contribution to journalArticle

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AU - Case, David

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AB - Xα multiple scattering calculations are reported for the d4 oxo complexes Fe(P)(py)(O)0, 1+(P = porphine, py = pyridine), models for the active sites of intermediates I and II of horseradish peroxidase. Orbital energy trends for the addition of pyridine and then oxygen to Fe(II) porphine are used to rationalize spin and oxidation states of these clusters. Particular attention is paid to comparisons with ENDOR spectral data on intermediate I. Our results suggest that both a and ir spin transfer to the ligands is important and that the spins localized at the FeO and porphyrin sites interact strongly.

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