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Closed Shell Iron(IV) Oxo Complex with an Fe–O Triple Bond: Computational Design, Synthesis, and Reactivity
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SYSNO ASEP 0534141 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Článek ve WOS Title Closed Shell Iron(IV) Oxo Complex with an Fe–O Triple Bond: Computational Design, Synthesis, and Reactivity Author(s) Andris, Erik (UOCHB-X) ORCID
Segers, K. (NL)
Mehara, J. (NL)
Rulíšek, Lubomír (UOCHB-X) RID, ORCID
Roithová, J. (NL)Source Title Angewandte Chemie - International Edition. - : Wiley - ISSN 1433-7851
Roč. 59, č. 51 (2020), s. 23137-23144Number of pages 7 s. Language eng - English Country DE - Germany Keywords ion spectroscop ; iron oxo complexes ; ligand design ; spin state Subject RIV CF - Physical ; Theoretical Chemistry OECD category Physical chemistry R&D Projects LTAUSA19148 GA MŠMT - Ministry of Education, Youth and Sports (MEYS) Method of publishing Open access Institutional support UOCHB-X - RVO:61388963 UT WOS 000585630800001 EID SCOPUS 85094186491 DOI 10.1002/anie.202009347 Annotation 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. Workplace Institute of Organic Chemistry and Biochemistry Contact asep@uochb.cas.cz ; Kateřina Šperková, Tel.: 232 002 584 ; Jana Procházková, Tel.: 220 183 418 Year of Publishing 2021 Electronic address https://doi.org/10.1002/anie.202009347
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