Exposing the oxygen‐centered radical character of the tetraoxido ruthenium(VIII) cation [RuO4]+
Abstract: The tetraoxido ruthenium(VIII) radical cation, [RuO4]+, should be a strong oxidizing agent, but has been difficult to produce and investigate so far. In our X-ray absorption spectroscopy study, in combination with quantum-chemical calculations, we show that [RuO4]+, produced via oxidation of ruthenium cations by ozone in the gas phase, forms the oxygen-centered radical ground state. The oxygen-centered radical character of [RuO4]+ is identified by the chemical shift at the ruthenium M3 edge, indicative of ruthenium(VIII), and by the presence of a characteristic low-energy transition at the oxygen K edge, involving an oxygen-centered singly-occupied molecular orbital, which is suppressed when the oxygen-centered radical is quenched by hydrogenation of [RuO4]+ to the closed-shell [RuO4H]+ ion. Hydrogen-atom abstraction from methane is calculated to be only slightly less exothermic for [RuO4]+ than for [OsO4]+
- Location
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Deutsche Nationalbibliothek Frankfurt am Main
- Extent
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Online-Ressource
- Language
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Englisch
- Notes
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ISSN: 1439-7641
- Event
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Veröffentlichung
- (where)
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Freiburg
- (who)
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Universität
- (when)
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2024
- Creator
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Silva Santos, Mayara da
Medel, Robert
Flach, Max
Ablyasova, Olesya S.
Timm, Martin
Issendorff, Bernd von
Hirsch, Konstantin
Zamudio-Bayer, Vicente
Hasenstab-Riedel, Sebastian
Lau, J. Tobias
- DOI
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10.1002/cphc.202300390
- URN
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urn:nbn:de:bsz:25-freidok-2458738
- Rights
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Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
- Last update
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25.03.2025, 1:54 PM CET
Data provider
Deutsche Nationalbibliothek. If you have any questions about the object, please contact the data provider.
Associated
- Silva Santos, Mayara da
- Medel, Robert
- Flach, Max
- Ablyasova, Olesya S.
- Timm, Martin
- Issendorff, Bernd von
- Hirsch, Konstantin
- Zamudio-Bayer, Vicente
- Hasenstab-Riedel, Sebastian
- Lau, J. Tobias
- Universität
Time of origin
- 2024
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