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Oxygen radical character in group 11 oxygen fluorides.

ABSTRACT: 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 3? - ground state with a biradical character. Two unpaired electrons are located mainly at the oxygen ligand in antibonding O-M ?* 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.

SUBMITTER: Li L

PROVIDER: S-EPMC5871800 | biostudies-other | 2018 Mar

REPOSITORIES: biostudies-other

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Oxygen radical character in group 11 oxygen fluorides.

Li Lin L Stüker Tony T Kieninger Stefanie S Andrae Dirk D Schlöder Tobias T Gong Yu Y Andrews Lester L Beckers Helmut H Riedel Sebastian S

Nature communications 20180328 1

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 OF<sub>2</sub> to form hypofluorites FOMF and group 11 oxygen metal fluorides OMF<sub>2</sub>, 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 photoly ...[more]

PMID: 29593258

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