Does hydrogen-bonding donation to manganese(IV)-oxo and iron(IV)-oxo oxidants affect the oxygen-atom transfer ability? a computational study

Latifi, Reza, Mala, Alhaji, Rybak‐Akimova, E. and de Visser, S. 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) , pp. 4058-4068. 10.1002/chem.201202811

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Abstract

Iron(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.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry Cardiff Catalysis Institute (CCI)
Publisher:	Wiley
ISSN:	0947-6539
Last Modified:	07 Jan 2022 02:38
URI:	https://orca.cardiff.ac.uk/id/eprint/111750

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