Mechanisms of O2 Activation by Mononuclear Non-Heme Iron Enzymes
Abstract
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 FeIV=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 FeIV=O intermediate and the geometric and electronic structure of this intermediate that enables its high reactivity and selectivity in product formation.
- Authors:
-
[1];
- Stanford University, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Stanford University, CA (United States)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Institutes of Health (NIH0
- OSTI Identifier:
- 1874263
- Grant/Contract Number:
- AC02-76SF00515; 40392
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Biochemistry
- Additional Journal Information:
- Journal Volume: 60; Journal Issue: 46; Journal ID: ISSN 0006-2960
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Solomon, Edward I., DeWeese, Dory E., and Babicz, Jeffrey T. Mechanisms of O2 Activation by Mononuclear Non-Heme Iron Enzymes. United States: N. p., 2021.
Web. doi:10.1021/acs.biochem.1c00370.
Solomon, Edward I., DeWeese, Dory E., & Babicz, Jeffrey T. Mechanisms of O2 Activation by Mononuclear Non-Heme Iron Enzymes. United States. https://doi.org/10.1021/acs.biochem.1c00370
Solomon, Edward I., DeWeese, Dory E., and Babicz, Jeffrey T. Thu .
"Mechanisms of O2 Activation by Mononuclear Non-Heme Iron Enzymes". United States. https://doi.org/10.1021/acs.biochem.1c00370. https://www.osti.gov/servlets/purl/1874263.
@article{osti_1874263,
title = {Mechanisms of O2 Activation by Mononuclear Non-Heme Iron Enzymes},
author = {Solomon, Edward I. and DeWeese, Dory E. and Babicz, Jeffrey T.},
abstractNote = {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 FeIV=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 FeIV=O intermediate and the geometric and electronic structure of this intermediate that enables its high reactivity and selectivity in product formation.},
doi = {10.1021/acs.biochem.1c00370},
journal = {Biochemistry},
number = 46,
volume = 60,
place = {United States},
year = {Thu Jul 15 00:00:00 EDT 2021},
month = {Thu Jul 15 00:00:00 EDT 2021}
}
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