24762-17-2Relevant articles and documents
The OsO3F+ and μ-F(OsO3F)2+ cations
Gerken, Michael,Dixon, David A.,Schrobilgen, Gary J.
, p. 259 - 277 (2002)
The fluoride ion donor properties of OsO3F2 have been investigated. The salts [OsO3F][AsF6], [OsO3F][HF]2[AsF6], μ-F(OsO3F)2[AsF6], [OsO3F][HF]2[SbF6], and [OsO3F][HF][SbF6] have been prepared by reaction of OsO3F2 with AsF5 and SbF5 in HF solvent and have been characterized in the solid state by Raman spectroscopy. The single-crystal X-ray diffraction studies of [OsO3F][AsF6] (P21/n, a = 7.0001(11) A, b = 11.0620(11) A, c = 8.8629(13) A, β = 92.270(7)°, Z = 4, and R1 = 0.0401 at -126 °C), [OsO3F][SbF6] (P21/c, a = 5.4772(14) A, b = 10.115(3) A, c = 12.234(3) A, β = 99.321(5)°, Z = 4, and R1 = 0.0325 at -173 °C), [OsO3F][HF]2[AsF6] (P21/n, a = 5.1491(9) A, b = 8.129(2) A, c = 19.636(7) A, β = 95.099(7)°, Z = 4, and R1 = 0.0348 at -117 °C), and [OsO3F][HF][SbF6] (Pc, a = 5.244(4) A, b = 9.646(6) A, c = 15.269(10) A, β = 97.154(13)°, Z = 4, and R1 = 0.0558 at -133 °C) have shown that the OsO3F+ cations exhibit strong contacts to the anions and HF solvent molecules giving rise to cyclic, dimeric structures in which the osmium atoms have coordination numbers of 6. The reaction of OsO3F2 with neat SbF5 yielded [OsO3F][Sb3F16], which has been characterized by 19F NMR spectroscopy in SbF5 and SO2CIF solvents and by Raman spectroscopy and single-crystal X-ray diffraction in the solid state (P421m, a = 10.076(6) A, c = 7.585(8) A, Z = 2, and R1 = 0.0858 at -113 °C). The weak fluoride ion basicity of the Sb3F16- anion resulted in an OsO3F+ cation (C3v point symmetry) that is well isolated from the anion and in which the osmium is four-coordinate. The geometrical parameters and vibrational frequencies of OsO3F+, ReO3F, μ-F(OsO3F)2+, [FO3Os - FPnF5)2, and (FO3Os - (HF)2 - FPnF5)2 (Pn = As, Sb) have been calculated using density functional theory methods.
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.
