Closed Shell Iron(IV) Oxo Complex with an Fe–O Triple Bond: Computational Design, Synthesis, and Reactivity
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F20%3A00534141" target="_blank" >RIV/61388963:_____/20:00534141 - isvavai.cz</a>
Result on the web
<a href="https://doi.org/10.1002/anie.202009347" target="_blank" >https://doi.org/10.1002/anie.202009347</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1002/anie.202009347" target="_blank" >10.1002/anie.202009347</a>
Alternative languages
Result language
angličtina
Original language name
Closed Shell Iron(IV) Oxo Complex with an Fe–O Triple Bond: Computational Design, Synthesis, and Reactivity
Original language description
Iron(IV)‐oxo intermediates in nature contain two unpaired electrons in the Fe–O antibonding orbitals, which are thought to contribute to their high reactivity. To challenge this hypothesis, we designed and synthesized closed‐shell singlet iron(IV) oxo complex [(quinisox)Fe(O)]+ (1+, quinisox‐H=(N‐(2‐(2‐isoxazoline‐3‐yl)phenyl)quinoline‐8‐carboxamide). We identified the quinisox ligand by DFT computational screening out of over 450 candidates. After the ligand synthesis, we detected 1+ in the gas phase and confirmed its spin state by visible and infrared photodissociation spectroscopy (IRPD). The Fe–O stretching frequency in 1+ is 960.5 cm−1, consistent with an Fe–O triple bond, which was also confirmed by multireference calculations. The unprecedented bond strength is accompanied by high gas‐phase reactivity of 1+ in oxygen atom transfer (OAT) and in proton‐coupled electron transfer reactions. This challenges the current view of the spin‐state driven reactivity of the Fe–O complexes.
Czech name
—
Czech description
—
Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
—
OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
<a href="/en/project/LTAUSA19148" target="_blank" >LTAUSA19148: Mono- and binuclear Fe, Cu active sites in biological systems: interplay between theory and experiment</a><br>
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2020
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Angewandte Chemie - International Edition
ISSN
1433-7851
e-ISSN
—
Volume of the periodical
59
Issue of the periodical within the volume
51
Country of publishing house
DE - GERMANY
Number of pages
7
Pages from-to
23137-23144
UT code for WoS article
000585630800001
EID of the result in the Scopus database
2-s2.0-85094186491