13774-85-1Relevant articles and documents
Smith, D. F.
, p. 899 - 899 (1963)
Synthesis and X-ray crystal structure of (OsO3F 2)2·2XeOF4 and the raman spectra of (OsO3F2)∞, (OsO3F 2)2, and (OsO3F2) 2·2XeOF4
Hughes, Michael J.,Mercier, Helene P.A.,Schrobilgen, Gary J.
, p. 4478 - 4490 (2009/09/24)
The adduct, (OsO3F2).2XeOF4, was synthesized by dissolution of the infinite chain polymer, (OsO3F 2), in XeOF4 solvent at room temperature followed by removal of excess XeOF4under dynamic vacuum at 0 °C. Continued pumping at 0°C resulted in removal of associated XeOF4, yielding (Os0 3F2)2, a new low-temperature phase of OsO3F2. Upon standing at 25 °C for 1/2 h, (Oso3F2)2 underwent a phase transition to the known monoclinic phase, (OsO 3F2). The title compounds, (OsO3F 2)∞ (OsO3F2)2, and (OsO 3F2)2.2XeOF4 have been characterized by low-temperature (-150 °C) Raman spectroscopy. Crystallization of (OsO3F2)2.2XeOF4 from XeOF 4 solution at O °C yielded crystals suitable for X-ray structure determination. The structural unit contains the (OsO3F 2)2 dimer in which the OsO3F3 units are joined by two Os-F-Os bridges having fluorine bridge atoms that are equidistant from the osmium centers (2.117(5) and 2.107(4) A). The dimer coordinates to two XeOF4molecules through OsF... Xe bridges in which the Xe... F distances (2.757(5) A) are significantly less than the sum of the Xe and F van der Waals radii (3.63 A). The (OsO3F2) 2 dimer has Ci symmetry in which each pseudo-octahedral OsO3F3 unit has a facial arrangement of oxygen ligands with XeOF4 molecules that are only slightly distorted from their gasphase C4v, symmetry. Quantum-chemical calculations using SVWN and B3LYP methods were employed to calculate the gas-phase geometries, natural bond orbital analyses, and vibrational frequencies of (OsO3F 2)2, (OsO3F2)2.2XeOF 4, XeOF4, OsO2F4, and (w-FOs0 3F2)2OsO3F~ to aid in the assignment of the experimental vibrational frequencies of (OsO3F 2)2, (OsO3F2)2.2XeOF 4, and (OsO3F2)∞ The vibrational modes of the low-temperature polymeric phase, (OsO3F2)∞ have been assigned by comparison with the calculated frequencies of (w-FOsO 3F2)2OsO3F-, providing more complete and reliable assignments than were previously available.
New syntheses and properties of XeO2F2, Cs+XeO2F3-, and NO2+[XeO2F3·nXeO 2F2]-
Christe, Karl O.,Wilson, William W.
, p. 3763 - 3768 (2008/10/08)
Alkali-metal nitrates and N2O5 are useful reagents for the stepwise replacement of two fluorine atoms by one oxygen atom in xenon fluorides or oxyfluorides. Thus, the reaction of an excess of XeF6 with CsNO3 yields XeOF4, FNO2, and CsXeF7 in high yield. With CsNO3 in excess, the primary products are CsXeOF5 and FNO2, and after longer reaction times some CsXeO2F3 is also formed. The reaction of CsNO3 with an excess of XeOF4 produces FNO2 and XeO2F2 in quantitative yield with a mixture of CsF and CsXeOF5 as the byproducts. Recrystallization of this CsF-CsXeOF5-XeO2F2 mixture from anhydrous HF provides a convenient synthesis for CsXeO2F3. The reaction of N2O5 with an excess of XeOF4 results in XeO2F2 and FNO2, thus providing a new safe synthesis for XeO2F2. Vibrational spectra of liquid, solid, and Ar-matrix-isolated XeO2F2 are reported. With FNO2, xenon dioxide difluoride forms an unstable NO2+[XeO2F3·nXeO 2F2]- adduct, which was characterized by Raman spectroscopy. The vibrational spectra of CsXeO2F3 were recorded and assigned. It is shown that the two oxygen atoms in XeO2F3- are cis and not trans to each other and that the Raman spectrum previously attributed to Cs+XeO2F3- is due to a Cs+[XeO2F3·nXeF2]- adduct.
