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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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Project description:As a result of the adaptation of life to an aerobic environment, nature has evolved a panoply of metalloproteins for oxidative metabolism and protection against reactive oxygen species. Despite the diverse structures and functions of these proteins, they share common mechanistic grounds. An open-shell transition metal like iron or copper is employed to interact with O2 and its derived intermediates such as hydrogen peroxide to afford a variety of metal-oxygen intermediates. These reactive intermediates, including metal-superoxo, -(hydro)peroxo, and high-valent metal-oxo species, are the basis for the various biological functions of O2-utilizing metalloproteins. Collectively, these processes are called oxygen activation. Much of our understanding of the reactivity of these reactive intermediates has come from the study of heme-containing proteins and related metalloporphyrin compounds. These studies not only have deepened our understanding of various functions of heme proteins, such as O2 storage and transport, degradation of reactive oxygen species, redox signaling, and biological oxygenation, etc., but also have driven the development of bioinorganic chemistry and biomimetic catalysis. In this review, we survey the range of O2 activation processes mediated by heme proteins and model compounds with a focus on recent progress in the characterization and reactivity of important iron-oxygen intermediates. Representative reactions initiated by these reactive intermediates as well as some context from prior decades will also be presented. We will discuss the fundamental mechanistic features of these transformations and delineate the underlying structural and electronic factors that contribute to the spectrum of reactivities that has been observed in nature as well as those that have been invented using these paradigms. Given the recent developments in biocatalysis for non-natural chemistries and the renaissance of radical chemistry in organic synthesis, we envision that new enzymatic and synthetic transformations will emerge based on the radical processes mediated by metalloproteins and their synthetic analogs.

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Oxygen radical character in group 11 oxygen fluorides.

Publications

Oxygen radical character in group 11 oxygen fluorides.

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