Closed Shell Iron(IV) Oxo Complex with an Fe–O Triple Bond: Computational Design, Synthesis, and Reactivity

0534141 - ÚOCHB 2021 RIV DE eng J - Článek v odborném periodiku
Andris, Erik - Segers, K. - Mehara, J. - Rulíšek, Lubomír - Roithová, J.
Closed Shell Iron(IV) Oxo Complex with an Fe–O Triple Bond: Computational Design, Synthesis, and Reactivity.
Angewandte Chemie - International Edition. Roč. 59, č. 51 (2020), s. 23137-23144. ISSN 1433-7851. E-ISSN 1521-3773
Grant CEP: GA MŠMT(CZ) LTAUSA19148
Institucionální podpora: RVO:61388963
Klíčová slova: ion spectroscop * iron oxo complexes * ligand design * spin state
Obor OECD: Physical chemistry
Impakt faktor: 15.336, rok: 2020
Způsob publikování: Open access
https://doi.org/10.1002/anie.202009347

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.
Trvalý link: http://hdl.handle.net/11104/0312440