Characterized cis-FeV(O)(OH) intermediate mimics enzymatic oxidations in the gas phase
| Autor: | Erik Andris, Jana Roithová, Rafael Navrátil, Margarida Borrell, Miquel Costas |
|---|---|
| Jazyk: | angličtina |
| Rok vydání: | 2019 |
| Předmět: |
0301 basic medicine
Oxygenase Stereochemistry Iron Science Catalitzadors Reactive intermediate General Physics and Astronomy Context (language use) 02 engineering and technology Article Catalysis General Biochemistry Genetics and Molecular Biology Bioinorganic chemistry Chemistry Physical and theoretical 03 medical and health sciences Spectroscopy and Catalysis Reactivity (chemistry) lcsh:Science chemistry.chemical_classification Multidisciplinary Catalysts General Chemistry Química bioinorgànica 021001 nanoscience & nanotechnology 3. Good health respiratory tract diseases 030104 developmental biology Enzyme chemistry Dihydroxylation Oxygenases lcsh:Q 0210 nano-technology Oxidation-Reduction Iron Compounds Fisicoquímica |
| Zdroj: | Nature Communications, Vol 10, Iss 1, Pp 1-9 (2019) Nature Communications, 10, 1-9 Nature Communications, 2019, vol. 10, núm. art. 901 Articles publicats (D-Q) Borrell Recasens, Margarida Andris, Erik Navrátil, Rafael Roithová, Jana Costas Salgueiro, Miquel 2019 Characterized cis-FeV(O)(OH) Intermediate Mimics Enzymatic Oxidations in the Gas Phase Nature Communications 10 Art. 901 1 9 DUGiDocs – Universitat de Girona instname Nature Communications Nature Communications, 10, 1, pp. 1-9 |
| ISSN: | 2041-1723 |
| Popis: | FeV(O)(OH) species have long been proposed to play a key role in a wide range of biomimetic and enzymatic oxidations, including as intermediates in arene dihydroxylation catalyzed by Rieske oxygenases. However, the inability to accumulate these intermediates in solution has thus far prevented their spectroscopic and chemical characterization. Thus, we use gas-phase ion spectroscopy and reactivity analysis to characterize the highly reactive [FeV(O)(OH)(5tips3tpa)]2+ (32+) complex. The results show that 32+ hydroxylates C–H bonds via a rebound mechanism involving two different ligands at the Fe center and dihydroxylates olefins and arenes. Hence, this study provides a direct evidence of FeV(O)(OH) species in non-heme iron catalysis. Furthermore, the reactivity of 32+ accounts for the unique behavior of Rieske oxygenases. The use of gas-phase ion characterization allows us to address issues related to highly reactive intermediates that other methods are unable to solve in the context of catalysis and enzymology. FeV(O)(OH) species have long been thought to play a role in a range of enzymatic oxidations, but their characterization has remained elusive. Here, using gas-phase ion spectroscopy, the authors characterize an FeV(O)(OH) species and find that its reactivity mimics that of Rieske oxygenases. |
| Databáze: | OpenAIRE |
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