Exposing the oxygen‐centered radical character of the tetraoxido ruthenium(VIII) cation [RuO4]+

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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]+

Standort
Deutsche Nationalbibliothek Frankfurt am Main
Umfang
Online-Ressource
Sprache
Englisch
Anmerkungen
ISSN: 1439-7641

Ereignis
Veröffentlichung
(wo)
Freiburg
(wer)
Universität
(wann)
2024
Urheber

DOI
10.1002/cphc.202300390
URN
urn:nbn:de:bsz:25-freidok-2458738
Rechteinformation
Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
Letzte Aktualisierung
25.03.2025, 13:54 MEZ

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