A Pseudotetrahedral Terminal Oxoiron(IV) Complex: Mechanistic Promiscuity in C−H Bond Oxidation Reactions
| Autor: | Alice Paskin, Katrin Warm, Peter Hildebrandt, Uwe Kuhlmann, Marcel Swart, Kallol Ray, Holger Dau, Michael Haumann, Eckhard Bill |
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| Přispěvatelé: | Ministerio de Economía y Competitividad (Espanya) |
| Rok vydání: | 2021 |
| Předmět: |
Steric effects
Oxidation-reduction reaction High-valent iron Stereochemistry Reactive intermediate 010402 general chemistry Hydrogen atom abstraction 01 natural sciences Catalysis bioinorganic chemistry Electron transfer high-valent iron Reacció d'oxidació-reducció hydrogen atom abstraction Research Articles enzyme models 010405 organic chemistry Ligand Chemistry General Medicine General Chemistry Química bioinorgànica electron transfer Bioinorganic Chemistry | Hot Paper 0104 chemical sciences Trigonal bipyramidal molecular geometry 540 Chemie und zugeordnete Wissenschaften Catalytic cycle ddc:540 ddc:660 500 Naturwissenschaften und Mathematik::540 Chemie::540 Chemie und zugeordnete Wissenschaften 660 Chemische Verfahrenstechnik und verwandte Technologien Research Article |
| Zdroj: | Angewandte Chemie (International Ed. in English) Angewandte Chemie-International Edition Angewandte Chemie International Edition, 2021, vol. undef, núm. undef, p. undef Articles publicats (D-Q) DUGiDocs – Universitat de Girona instname |
| ISSN: | 1521-3773 1433-7851 |
| DOI: | 10.1002/anie.202015896 |
| Popis: | 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). A highly reactive S=2 pseudotetrahedral oxoiron(IV) complex 2 supported by a sterically demanding 1,4,7‐tri‐tert‐butyl‐1,4,7‐triazacyclononane ligand has been synthesized and spectroscopically characterized as one of the best electronic and functional models for a biological oxoiron(IV) intermediate of taurine dioxygenase (TauD‐J). |
| Databáze: | OpenAIRE |
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