Atoms, Inorganic Radicals, and Radicals in Metal Complexes

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Assignments are indicated and unassigned features are marked by asterisks. Further spectra are provided in the SI. For both hypofluorites these two stretching bands are clearly assigned. This observation indicates a rather strong interaction of this species with the solid hosts. We noticed a strong dependence of the intensity of the hypofluorite bands on experimental conditions, such as the choice of the matrix gas, its OF 2 concentration, and the amount of the laser energy used for metal ablation. The FMOF species are found to be highly photo-sensitive.

Bands of the OF radical, located at Another source of OF radicals is the photo-decomposition of the OF 2 precursor during the deposition. Furthermore, the photo-decomposition of OF radicals 26 by subsequent near-UV radiation will produce free F and O radicals which exhibit a limited mobility within the solid matrices and initiate secondary reactions with metal species trapped nearby.

In these experiments none of the bands assigned to an oxygen-containing species appeared. They agree well with previously reported experimental and calculated ones 27 , Our present results show a weak band at The gas-phase value for the 63 CuF IR band was reported at Calculated structures.

Bond lengths in pm and angle in degree. The IR spectra obtained for the gold species in solid Ne Fig. These observations suggest that the band at Our tentative assignment of the OAuF species is supported by coupled-cluster calculations. In the reaction of laser ablated silver atoms with a mixture of 16 OF 2 and 18 OF 2 we observed two additional weak bands at This is a characteristic feature of a so called inverted ligand field 36 , 37 , 38 , for which the binary group 11 oxides such as the [OAuO] — anion 14 may serve as an additional example.

The computed spin density of 1. Computed Spin Density. Spin density iso-surface at 0.

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These species were always present in the deposits. It is therefore reasonable that this reaction was observed using neon matrices by substitution of a weakly bound Ne atom in a NeAuF complex, but not in solid argon where the ArAuF complex was found to be one of the main reaction products Fig. As pointed out by a referee we noticed that such a breakdown of the conventional Lewis electron—pair model is not a unique phenomenon of group 11 oxygen compounds.

One closely related example is the recently investigated oxygen-centered OHgF radical 39 , but also other transition metal terminal oxo complexes bearing terminal oxygen-centered radicals have been predicted 22 , 23 , 24 , Terminal oxygen radicals have also been found to occur in metal oxide clusters of early transition metals, when these metals are in their highest oxidation state.

Such oxide clusters were found to be crucial intermediates in catalytic oxidation reactions 41 , The isolation of these novel species in rare-gas matrices allowed a direct spectroscopic investigation of group 11 compounds bearing a terminal oxygen ligand in a condensed phase. The new oxygen fluorides are likely formed by photolysis of the initially prepared hypofluorites.

Metal complexes of thiazyl radicals

For the 2 B 2 ground state of the OMF 2 compounds only an O—M single bond arises and a significant spin-density contribution was found at the oxygen atom as well. The radical character of the terminal oxygen ligand in these group 11 fluorides can be explained with an inverted ligand field, which previously has also been suggested for the related binary group 11 oxides 14 , 19 , It turns out that the investigation of these novel oxygen fluorides is a challenge for prospective experimental and high-level quantum chemical studies. The OF 2 and ablated metal atoms and their reaction products have been trapped in rare-gas matrices on a cold rhodium-plated mirror.

Ray, K. Terminal oxo and imido transition-metal complexes of groups Hay-Motherwell, R. Synthesis and X-ray crystal structure of oxotrimesityliridium V. Polyhedron 12 , — Poverenov, E. Evidence for a terminal Pt IV -oxo complex exhibiting diverse reactivity.

Nature , — Efremenko, I. DFT study of the structure and reactivity of the terminal Pt IV -oxo complex bearing no electron-withdrawing ligands. Pellarin, K. Oxidation of dimethylplatinum II complexes with a dioxirane: the viability of oxoplatinum IV intermediates. Organometallics 31 , — Lippert, B. More of a misunderstanding than a real mismatch? Platinum and its affinity for aqua, hydroxido, and oxido ligands. Wang, B. Synthesis and reactivity of a mononuclear non-haem cobalt IV -oxo complex. Tsvetkov, N.

Asami, S. Isolation and characterization of radical anions derived from a boryl-substituted diphosphene. Lichtenberg, C. Wang, X. Infrared spectra of antimony and bismuth hydrides in solid matrixes. A , — Cho, H. Kretschmer, R.

One-, two-, and three-electron reduction of a cyclic alkyl- amino carbene-SbCl 3 adduct. Ishida, S. Persistent antimony- and bismuth-centered radicals in solution. Schwamm, R.

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    Nomenclature of Inorganic Chemistry

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    8. Organometallics 33 , — Kost, D. The validity of approximate equations for k c in dynamic nuclear magnetic resonance. Petrie, M. Molecular double-bond covalent radii for elements Li—E Fischer, R. Download references. We also thank E. Jones TU Braunschweig, Germany for the crystallographic data measurement, procession and the solution of 3.