Raman and IR spectra of matrix isolated OsO₃F₂ AND OsO₄: The molecular shape of monomeric OsO₃F₂

Abstract

This paper reports fundamental vibration frequencies for molecular OS03Fz and o s o 4 isolated in argon matrices at low temperatures. Os03Fz is shown to have D3h symmetry on the basis of Raman and IR selection rules, and this conclusion is confirmed by the results of ' 8 0 enrichment studies which demonstrate the presence of an oso3 unit containing three equivalent oxygens. The argon matrix frequencies are 946.5 ( A ; ) , 928.5 (E'), 646 (A;), 619 ( A ; ) 348 (E"), 316.5 (E') 258 ( A ; ) and 206 (E') cm-l. High resolution spectra are also reported for matrix isolated oS1604 (~1963, vz 332, v3 956, and v4 327 cm-I) and for ' 8 0 enriched oso4 species.

Formation of carbyne complexes in reactions of laser-ablated Os atoms with halomethanes: characterization by C–H(X) and Os–H(X) stretching absorptions and computed structures

“…We are not aware of infrared spectra of binary osmium fluorides, but the matrix-isolated OsO 3 F 2 molecule exhibits Os-F stretching modes in this region at 619 and 646 cm -1 . 23 Another y absorption at 521.5 cm -1 has its CH 2 FCl counterpart at 568.7 cm -1 , but its D counterpart is unfortunately beyond our observation range. It is assigned to the HCOs bending mode due to the frequency and sizable shifts (Tables S1 and S2 †).…”

On the Highest Oxidation States of Metal Elements in MO4 Molecules (M = Fe, Ru, Os, Hs, Sm, and Pu)

“… a From DFT-B3LYP calculations. b Metastable isomers are indicated by *. c Values in [ ] are scaled by empirical factor 0.9698, for comparison with experimental data in ⟨ ⟩. − d Here M<O 2 means M­(η 2 -O 2 ), i.e., M is side-on coordinated by the O 2 species. …”

Calculating the partitioning of the isotopes of Mo between oxidic and sulfidic species in aqueous solution

“…This conclusion is supported by the good agreement of calculation and experiment for related molecules. For example, for gas-phase OsO 4 we obtain frequencies at the polarized SBK B3LYP level of 326, 330, 972 and 998 cm Ϫ1 for the four different normal modes while experimental values from matrix isolation IR and Raman spectroscopy are 333, 329, 961 and 965 cm Ϫ1 (Beattie et al, 1976). In Table 2 we give the frequencies calculated for the 100 Mo and 92 Mo isotopomers of MoO 4 Ϫ2 for the 3 (t 2 asymmetric stretch) and 4 (t 2 bend) modes, those modes in which the central atom, Mo, moves.…”