π-Frontier molecular orbitals in S = 2 ferryl species and elucidation of their contributions to reactivity

Martin Srnec, Shaun D. Wong, Jason England, Lawrence Que, Edward I. Solomon

Research output: Contribution to journalArticlepeer-review

59 Scopus citations

Abstract

S = 2 FeIV=O species are key intermediates in the catalysis of most nonheme iron enzymes. This article presents detailed spectroscopic and high-level computational studies on a structurallydefined S = 2 FeIV =O species that define its frontier molecular orbitals, which allow its high reactivity. Importantly, there are both π- and σ-channels for reaction, and both are highly reactive because they develop dominant oxyl character at the transition state. These π- and σ-channels have different orientation dependences defining how the same substrate can undergo different reactions (H-atom abstraction vs. electrophilic aromatic attack) with Fe IV =O sites in different enzymes, and how different substrates can undergo different reactions (hydroxylation vs. halogenation) with an Fe IV =O species in the same enzyme.

Original languageEnglish (US)
Pages (from-to)14326-14331
Number of pages6
JournalProceedings of the National Academy of Sciences of the United States of America
Volume109
Issue number36
DOIs
StatePublished - Sep 4 2012

Keywords

  • Density functional calculations
  • Excited-state potential energy surfaces
  • Magnetic circular dichroism
  • Multiconfigurational calculations
  • Reaction coordinates

Fingerprint Dive into the research topics of 'π-Frontier molecular orbitals in S = 2 ferryl species and elucidation of their contributions to reactivity'. Together they form a unique fingerprint.

Cite this