Does Hydrogen‐Bonding Donation to Manganese(IV)–Oxo and Iron(IV)–Oxo Oxidants Affect the Oxygen‐Atom Transfer Ability? A Computational Study
10.1002/chem.201202811
Crossref journal-article
Wiley
Chemistry – A European Journal (311)
Abstract

AbstractIron(IV)–oxo intermediates are involved in oxidations catalyzed by heme and nonheme iron enzymes, including the cytochromes P450. At the distal site of the heme in P450 Compound I (FeIV–oxo bound to porphyrin radical), the oxo group is involved in several hydrogen‐bonding interactions with the protein, but their role in catalysis is currently unknown. In this work, we investigate the effects of hydrogen bonding on the reactivity of high‐valent metal–oxo moiety in a nonheme iron biomimetic model complex with trigonal bipyramidal symmetry that has three hydrogen‐bond donors directed toward a metal(IV)–oxo group. We show these interactions lower the oxidative power of the oxidant in reactions with dehydroanthracene and cyclohexadiene dramatically as they decrease the strength of the OH bond (BDEOH) in the resulting metal(III)–hydroxo complex. Furthermore, the distal hydrogen‐bonding effects cause stereochemical repulsions with the approaching substrate and force a sideways attack rather than a more favorable attack from the top. The calculations, therefore, give important new insights into distal hydrogen bonding, and show that in biomimetic, and, by extension, enzymatic systems, the hydrogen bond may be important for proton‐relay mechanisms involved in the formation of the metal–oxo intermediates, but the enzyme pays the price for this by reduced hydrogen atom abstraction ability of the intermediate. Indeed, in nonheme iron enzymes, where no proton relay takes place, there generally is no donating hydrogen bond to the iron(IV)–oxo moiety.

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Latifi, R., Sainna, M. A., Rybak‐Akimova, E. V., & de Visser, S. P. (2013). Does Hydrogen‐Bonding Donation to Manganese(IV)–Oxo and Iron(IV)–Oxo Oxidants Affect the Oxygen‐Atom Transfer Ability? A Computational Study. Chemistry – A European Journal, 19(12), 4058–4068. Portico.

Authors 4
  1. Reza Latifi (first)
  2. Mala A. Sainna (additional)
  3. Elena V. Rybak‐Akimova (additional)
  4. Sam P. de Visser (additional)
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Dates
Type When
Created 12 years, 7 months ago (Jan. 30, 2013, 5:32 a.m.)
Deposited 1 year, 10 months ago (Oct. 16, 2023, 8:18 p.m.)
Indexed 2 months, 1 week ago (June 20, 2025, 4:08 a.m.)
Issued 12 years, 7 months ago (Jan. 30, 2013)
Published 12 years, 7 months ago (Jan. 30, 2013)
Published Online 12 years, 7 months ago (Jan. 30, 2013)
Published Print 12 years, 5 months ago (March 18, 2013)
Funders 0

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@article{Latifi_2013, title={Does Hydrogen‐Bonding Donation to Manganese(IV)–Oxo and Iron(IV)–Oxo Oxidants Affect the Oxygen‐Atom Transfer Ability? A Computational Study}, volume={19}, ISSN={1521-3765}, url={http://dx.doi.org/10.1002/chem.201202811}, DOI={10.1002/chem.201202811}, number={12}, journal={Chemistry – A European Journal}, publisher={Wiley}, author={Latifi, Reza and Sainna, Mala A. and Rybak‐Akimova, Elena V. and de Visser, Sam P.}, year={2013}, month=jan, pages={4058–4068} }