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Journal Article

A Pseudotetrahedral Terminal Oxoiron(IV) Complex: Mechanistic Promiscuity in C‐H bond Oxidation Reactions

Authors

Ray,  Kallol
External Organizations;

Warm,  Katrin
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/persons/resource/apaskin

Paskin,  Alice
0 Pre-GFZ, Departments, GFZ Publication Database, Deutsches GeoForschungsZentrum;

Kuhlmann,  Uwe
External Organizations;

Bill,  Eckhard
External Organizations;

Swart,  Marcel
External Organizations;

Haumann,  Michael
External Organizations;

Dau,  Holger
External Organizations;

Hildebrandt,  Peter
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Citation

Ray, K., Warm, K., Paskin, A., Kuhlmann, U., Bill, E., Swart, M., Haumann, M., Dau, H., Hildebrandt, P. (2021): A Pseudotetrahedral Terminal Oxoiron(IV) Complex: Mechanistic Promiscuity in C‐H bond Oxidation Reactions. - Angewandte Chemie-International Edition, 60, 12, 6752-6756.
https://doi.org/10.1002/anie.202015896


Cite as: https://gfzpublic.gfz-potsdam.de/pubman/item/item_5005654
Abstract
S=2 oxoiron(IV) species act as reactive intermediates in the catalytic cycle of nonheme iron oxygenases. The few available synthetic S=2 FeIV=O complexes known to date are often limited to trigonal bipyramidal and very rarely to octahedral geometries. Herein we describe the generation and characterization of an S=2 pseudotetrahedral FeIV=O complex 2 supported by the sterically demanding 1,4,7‐tri‐tert‐butyl‐1,4,7‐triazacyclononane ligand. Complex 2 is a very potent oxidant in hydrogen atom abstraction (HAA) reactions with large non‐classical deuterium kinetic isotope effects, suggesting hydrogen tunneling contributions. For sterically encumbered substrates, direct HAA is impeded and an alternative oxidative asynchronous proton‐coupled electron transfer mechanism prevails, which is unique within the nonheme oxoiron community. The high reactivity and the similar spectroscopic parameters make 2 one of the best electronic and functional models for a biological oxoiron(IV) intermediate of taurine dioxygenase (TauD‐J).