Direct Spectroscopic Confirmation of the Oxygen‐Centered Diradical Character of the Tetraoxidorhenium(VII) Cation [Re(O)4]+
Year: 2024
Type: article
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,O4]+ 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,O4]+ to perform two consecutive hydrogen‐atom abstraction reactions from methane, and demonstrates that pentaatomic [Re,O4]+ combines a metal center in its highest oxidation state with two oxygen‐centered radical ligands in a highly reactive species.
DOI: 10.18452/31413
Authors: Da Silva Santos, Mayara, Medel, Robert, Kruse, Simon, Flach, Max, Ablyasova, Olesya S., Timm, Martin, Von Issendorff, Bernd, Hirsch, Konstantin, Zamudio‐Bayer, Vicente, Riedel, Sebastian, Lau, J. Tobias
Language: English
Subfield: Inorganic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W6888064535
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