Direct Spectroscopic Confirmation of the Oxygen‐Centered Diradical Character of the Tetraoxidorhenium(VII) Cation [Re(O)<sub>4</sub>]<sup>+</sup>
Abstract Mononuclear inorganic diradical species are scarce. Here, we confirm, via X‐ray absorption spectroscopy in the gas phase combined with computational studies, the oxygen‐centered diradical character of the tetraoxidorhenium(VII) cation. A dioxido‐superoxido isomer, close in energy to the diradical, is also found, where rhenium appears in its rare oxidation state of +6. Addition of one or two hydrogen atoms to [Re,O 4 ] + forms hydroxido ligands, and strongly disfavors isomers with any oxygen‐oxygen bond. This adds spectroscopic characterization of the rhenium oxidation state and the nature of ligands to the known ability of [Re,O 4 ] + to perform two consecutive hydrogen‐atom abstraction reactions from methane, and demonstrates that pentaatomic [Re,O 4 ] + combines a metal center in its highest oxidation state with two oxygen‐centered radical ligands in a highly reactive species.
Authors
- Sebastian L. Riedel (ORCID: https://orcid.org/0000-0003-1373-417X)
- Bernd von Issendorff (ORCID: https://orcid.org/0000-0002-4358-4494)
- Konstantin Hirsch (ORCID: https://orcid.org/0000-0001-5050-3026)
- Schoen W Kruse (ORCID: https://orcid.org/0009-0007-1970-2802)
- Olesya S. Ablyasova (ORCID: https://orcid.org/0009-0009-1373-172X)
- Max Flach (ORCID: https://orcid.org/0000-0002-5327-1555)
- Robert Medel (ORCID: https://orcid.org/0000-0001-6134-0437)
- Martin Timm (ORCID: https://orcid.org/0000-0003-4901-203X)
- J. Tobias Lau (ORCID: https://orcid.org/0000-0003-0976-6902)
- Vicente Zamudio‐Bayer (ORCID: https://orcid.org/0000-0002-4038-0584)
- Mayara da Silva Santos (ORCID: https://orcid.org/0000-0003-4439-6441)
Institutions
- University of Freiburg (DE)
- Helmholtz-Zentrum Berlin für Materialien und Energie (DE)
- Humboldt-Universität zu Berlin (DE)
- Freie Universität Berlin (DE)
Publication Details
- Journal
- Chemistry - Methods
- Published
- 2024-10-25
- DOI
- https://doi.org/10.1002/cmtd.202400023
- Primary Topic
- Lanthanide and Transition Metal Complexes
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- Deutsche Forschungsgemeinschaft
- Bundesministerium für Bildung und Forschung
- Freie Universität Berlin
- Helmholtz-Zentrum Berlin für Materialien und Energie
- H2020 European Research Council