Synthesis, Structural Characterization, and Computational Study of the Strong Oxidant Salt [XeOTeF5][Sb(OTeF5)6]·SO2ClF

详细信息    查看全文

• 作者：Hé ; lè ; ne P. A. Mercier ; Matthew D. Moran ; Jeremy C. P. Sanders ; Gary J. Schrobilgen ; and R. J. Suontamo
• 刊名：Inorganic Chemistry
• 出版年：2005
• 出版时间：January 10, 2005
• 年：2005
• 卷：44
• 期：1
• 页码：49 - 60
• 全文大小：274K
• 年卷期：v.44,no.1(January 10, 2005)
• ISSN：1520-510X

文摘

The strong oxidant salt [XeOTeF₅][Sb(OTeF₅)₆]·SO₂ClF has been synthesized by reaction of stoichiometric amountsof Xe(OTeF₅)₂ and Sb(OTeF₅)₃ in SO₂ClF solution at -78 C and characterized in SO₂ClF solution by low-temperature¹⁷O, ¹⁹F, ¹²¹Sb, ¹²⁵Te, and ¹²⁹Xe NMR spectroscopy, showing the Xe···O donor-acceptor bond XeOTeF₅⁺·SO₂ClFadduct-cation to be labile at temperatures as low as -80 C. The salt crystallizes from SO₂ClF as [XeOTeF₅][Sb(OTeF₅)₆]·SO₂ClF, and the low-temperature crystal structure was obtained: triclinic, P, a = 9.7665(5) Å, b =9.9799(4) Å, c = 18.5088(7) Å, = 89.293(2), = 82.726(2), = 87.433(3), V = 1787.67(13) ų, Z = 2,and R₁ = 0.0.0451 at -173 C. Unlike MF₆^- in [XeF][MF₆] (e.g., M = As, Sb, Bi) and [XeOTeF₅][AsF₆], theSb(OTeF₅)₆^- anion is significantly less basic and does not interact with the coordinately unsaturated xenon(II)cation. Rather, the XeOTeF₅⁺ cation and weak Lewis base, SO₂ClF, interact by coordination of an oxygen atom ofSO₂ClF to xenon [Xe···O, 2.471(5) Å]. The XeOTeF₅⁺·SO₂ClF adduct-cation has also been studied by low-temperatureRaman spectroscopy, providing frequencies that have been assigned to adducted SO₂ClF. The solid-state Ramanspectra of XeOTeF₅⁺·SO₂ClF and Sb(OTeF₅)₆^- have been assigned with the aid of electronic structure calculations.In addition to optimized geometries and vibrational frequencies, theoretical data, including gas-phase donor-acceptorbond energies, natural bond orbital (NBO) analyses, and topological analyses based on electron localization functions(ELF), provide descriptions of the bonding in XeOTeF₅⁺·SO₂ClF and related systems. The quantum mechanicalcalculations provided consistent trends for the relative strengths of the Xe···O donor-acceptor bond in XeOTeF₅⁺·SO₂ClF and ion-pair bonds in [XeL][MF₆] (L = F, OTeF₅; M = As, Sb), with the Xe···O bond of XeOTeF₅⁺·SO₂ClFbeing the weakest in the series.