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Proc Natl Acad Sci U S A. 2012 Sep 4;109(36):14326-31. doi: 10.1073/pnas.1212693109. Epub 2012 Aug 20.

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

Author information

1
Department of Chemistry, Stanford University, Stanford, CA 94305, USA.

Abstract

S = 2 Fe(IV) ═ 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 structurally-defined S = 2 Fe(IV) ═ 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.

PMID:
22908238
PMCID:
PMC3437891
DOI:
10.1073/pnas.1212693109
[Indexed for MEDLINE]
Free PMC Article

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