Characterized cis-Fe(+V)(O)(OH) intermediate mimics enzymatic oxidations in the gas phase

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F19%3A10394774" target="_blank" >RIV/00216208:11310/19:10394774 - isvavai.cz</a>

Result on the web

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=h8lkGwvgZx" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=h8lkGwvgZx</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1038/s41467-019-08668-2" target="_blank" >10.1038/s41467-019-08668-2</a>

Result language

angličtina

Original language name

Characterized cis-Fe(+V)(O)(OH) intermediate mimics enzymatic oxidations in the gas phase

Original language description

Fe(+V)(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 [Fe(+V)(O)(OH)((5tips3)tpa)](2+) (3(2+)) complex. The results show that 3(2+) 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 Fe(+V)(O) (OH) species in non-heme iron catalysis. Furthermore, the reactivity of 3(2+) 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.

Czech name

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Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

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OECD FORD branch

10401 - Organic chemistry

Project

—

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2019

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Nature Communications [online]

ISSN

2041-1723

e-ISSN

—

Volume of the periodical

10

Issue of the periodical within the volume

Feb 22

Country of publishing house

GB - UNITED KINGDOM

Number of pages

9

Pages from-to

901

UT code for WoS article

000459403800006

EID of the result in the Scopus database

2-s2.0-85062028876