Mechanisms of O2 Activation by Mononuclear Non-Heme Iron Enzymes

Solomon, Edward I.; DeWeese, Dory E.; Babicz, Jeffrey T.

doi:10.1021/acs.biochem.1c00370

Title: Mechanisms of O₂ Activation by Mononuclear Non-Heme Iron Enzymes

Journal Article · 15 July 2021 · Biochemistry

DOI: https://doi.org/10.1021/acs.biochem.1c00370 · OSTI ID:1874263

^[1]; DeWeese, Dory E. ^[2]; Babicz, Jeffrey T. ^[2]

Stanford University, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Stanford University, CA (United States)

We report two major subclasses of mononuclear non-heme ferrous enzymes use two electron-donating organic cofactors (α-ketoglutarate or pterin) to activate O2 to form Fe^IV=O intermediates that further react with their substrates through hydrogen atom abstraction or electrophilic aromatic substitution. New spectroscopic methodologies have been developed, enabling the study of the active sites in these enzymes and their oxygen intermediates. Coupled to electronic structure calculations, the results of these spectroscopies provide fundamental insight into mechanism. This Perspective summarizes the results of these studies in elucidating the mechanism of dioxygen activation to form the Fe^IV=O intermediate and the geometric and electronic structure of this intermediate that enables its high reactivity and selectivity in product formation.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: National Institutes of Health (NIH0; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1874263

Journal Information:: Biochemistry, Journal Name: Biochemistry Journal Issue: 46 Vol. 60; ISSN 0006-2960

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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