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Oxygen radical character in group 11 oxygen fluorides

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Lin Li, Tony Stüker, Stefanie Kieninger, Dirk Andrae, Tobias Schlöder, Yu Gong, Lester Andrews, Helmut Beckers and Sebastian Riedel – 2018

Transition metal complexes bearing terminal oxido ligands are quite common, yet group 11 terminal oxo complexes remain elusive. Here we show that excited coinage metal atoms M (M = Au, Ag, Cu) react with OF₂ to form hypofluorites FOMF and group 11 oxygen metal fluorides OMF₂, OAuF and OAgF. These compounds have been characterized by IR matrix-isolation spectroscopy in conjunction with state-of-the-art quantum-chemical calculations. The oxygen fluorides are formed by photolysis of the initially prepared hypofluorites. The linear molecules OAgF and OAuF have a ³Σ ⁻ ground state with a biradical character. Two unpaired electrons are located mainly at the oxygen ligand in antibonding O−M π* orbitals. For the ²B₂ ground state of the OMᴵᴵᴵF₂ compounds only an O−M single bond arises and a significant spin-density contribution was found at the oxygen atom as well.

Titel
Oxygen radical character in group 11 oxygen fluorides
Verfasser
Lin Li, Tony Stüker, Stefanie Kieninger, Dirk Andrae, Tobias Schlöder, Yu Gong, Lester Andrews, Helmut Beckers and Sebastian Riedel
Datum
2018
Erschienen in
Nat. Commun. 2018, 9, 1267
Zitierweise
DOI: 10.1038/s41467-018-03630-0
Sprache
eng