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

Kód výsledku v 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>

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

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

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

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

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10401 - Organic chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2019

Kód důvěrnosti údajů

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

Název periodika

Nature Communications [online]

ISSN

2041-1723

e-ISSN

—

Svazek periodika

10

Číslo periodika v rámci svazku

Feb 22

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

9

Strana od-do

901

Kód UT WoS článku

000459403800006

EID výsledku v databázi Scopus

2-s2.0-85062028876