Title
π-Frontier molecular orbitals in S = 2 ferryl species and elucidation of their contributions to reactivity
Author
Martin Srnec, Shaun D. Wong, Jason England, Lawrence Que, Jr., Edward I. Solomon
Year
2012
Journal
PNAS
Abstract
S ¼ 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 ¼ 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 FeIV═O sites in different enzymes, and how different substrates can undergo different reactions (hydroxylation vs. halogenation) with an FeIV═O species in the same enzyme.
Full Article
Instrument
J-810
Keywords
Magnetic circular dichroism, Near infrared, Coordination chemistry, Biochemistry