Unique structural and electronic features of perferryl-oxo oxidant in cytochrome P450

Hiroshi Isobe, Syusuke Yamanaka, Mitsutaka Okumura, Kizashi Yamaguchi, Jiro Shimada

Research output: Contribution to journalArticlepeer-review

21 Citations (Scopus)


We have performed hybrid density functional theory (DFT) calculations on the geometric and electronic structures of low-lying doublet and quartet ferryl-oxo [Fe(IV)=O] oxidants and a doublet perferryl-oxo [Fe(V)=O] oxidant in Cytochrome P450. Fully optimized structures of compound I models have been determined, and the proper symmetry of wave functions has been restored by the spin-projection technique. The results show that the perferryl-oxo species is relatively low lying, as compared with the excited state of the ferryl-oxo species, if the iron-oxo bond is properly described as the mixing of several appropriate excited electronic configurations to minimize electron repulsion. This means that the perferryl-oxo species is virtually in a mixed-valent resonance state, ↑Fe(V)=O ↔ ↑Fe(IV)•↑-↔•O, containing a highly reactive pπ atomic oxygen radical. The anionic thiolate ligand acts as a Lewis δ base and functions to achieve the stability of the perferryl-oxo complex and to activate the oxo ligand trans to it by asymmetric bond distortion along the O-Fe-S axis by lengthening the Fe-O bond and shortening the Fe-S bond, prior to the hydrogen-atom abstraction from the substrate.

Original languageEnglish
Pages (from-to)10730-10738
Number of pages9
JournalJournal of Physical Chemistry B
Issue number36
Publication statusPublished - Sept 15 2011
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry


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