DOI: 10.1073/pnas.0704191104. Substrate activation for O <sub>2</sub> reactions by oxidized metal centers in biology

Substrate activation for O 2 reactions by oxidized metal centers in biology

10.1073/pnas.0704191104

Crossref journal-article

Proceedings of the National Academy of Sciences

Proceedings of the National Academy of Sciences (341)

Abstract

The uncatalyzed reactions of O 2 (S = 1) with organic substrates (S = 0) are thermodynamically favorable but kinetically slow because they are spin-forbidden and the one-electron reduction potential of O 2 is unfavorable. In nature, many of these important O 2 reactions are catalyzed by metalloenzymes. In the case of mononuclear non-heme iron enzymes, either Fe II or Fe III can play the catalytic role in these spin-forbidden reactions. Whereas the ferrous enzymes activate O 2 directly for reaction, the ferric enzymes activate the substrate for O 2 attack. The enzyme–substrate complex of the ferric intradiol dioxygenases exhibits a low-energy catecholate to Fe III charge transfer transition that provides a mechanism by which both the Fe center and the catecholic substrate are activated for the reaction with O 2 . In this Perspective, we evaluate how the coupling between this experimentally observed charge transfer and the change in geometry and ligand field of the oxidized metal center along the reaction coordinate can overcome the spin-forbidden nature of the O 2 reaction.

Bibliography

Pau, M. Y. M., Lipscomb, J. D., & Solomon, E. I. (2007). Substrate activation for O 2 reactions by oxidized metal centers in biology. Proceedings of the National Academy of Sciences, 104(47), 18355â18362.

Authors 3

Monita Y. M. Pau (first)
John D. Lipscomb (additional)
Edward I. Solomon (additional)

References 39 Referenced 103

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Dates

Type	When
Created	17 years, 9 months ago (Nov. 14, 2007, 9:19 p.m.)
Deposited	3 years, 4 months ago (April 12, 2022, 4:39 p.m.)
Indexed	1 week, 1 day ago (Aug. 23, 2025, 1:03 a.m.)
Issued	17 years, 9 months ago (Nov. 20, 2007)
Published	17 years, 9 months ago (Nov. 20, 2007)
Published Online	17 years, 9 months ago (Nov. 20, 2007)
Published Print	17 years, 9 months ago (Nov. 20, 2007)

Funders 0

None

BibTeX

@article{Pau_2007, title={Substrate activation for O 2 reactions by oxidized metal centers in biology}, volume={104}, ISSN={1091-6490}, url={http://dx.doi.org/10.1073/pnas.0704191104}, DOI={10.1073/pnas.0704191104}, number={47}, journal={Proceedings of the National Academy of Sciences}, publisher={Proceedings of the National Academy of Sciences}, author={Pau, Monita Y. M. and Lipscomb, John D. and Solomon, Edward I.}, year={2007}, month=nov, pages={18355–18362} }

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