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首页> 外文学位 >Oxide and oxide fluorides of xenon(IV) and new developments in xenon(II), and krypton(II) chemistry.
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Oxide and oxide fluorides of xenon(IV) and new developments in xenon(II), and krypton(II) chemistry.

机译：氙（IV）的氧化物和氧化物氟化物以及氙（II）和k（II）化学的新进展。

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摘要

This Thesis extends the fundamental chemistry of the noble-gas elements, namely, xenon and krypton. More specifically, the chemistry of Xe(IV) has been extended by the synthesis and characterization of Xe(IV) oxide and oxide fluoride derivatives. The syntheses of XeOF2, F2OXeN≡CCH 3, and XeOF2 ˙nHF and their structural characterizations are described. All three compounds are endothermic and explosive at temperatures approaching 0 °C. Although XeOF2 had been previously reported, it had not been isolated as a pure compound. Xenon oxide difluoride has now been characterized in CH3CN solution by 19F, 17O, and 129Xe NMR spectroscopy and XeOF2, F2OXeN≡CCH3, and XeOF2 ˙ nHF have been characterized in the solid-state by Raman spectroscopy.;The [H(OXeF2)n][AsF6] and [FXeII(OXeIVF2)n][AsF6] (n = 1, 2) salts have been synthesized and structurally characterized in the solid state by low-temperature Raman spectroscopy. The chain length of each cation is limited to one or two OXeF2 subunits, which are oxygen-bridged and are strongly ion-paired with the AsF6 - anion. The reaction of XeOF2 ˙xHF in superacidic HF/SbF5 solvent mixtures resulted in a mixture of ([XeF3 ˙HF][Sb2F11])2·[H 5F4][SbF6], [XeF3 ˙HF][Sb 2F11], and [XeF3][SbF6].;The syntheses and structural characterizations of [XOF2][AsF 6] (X = Cl, Br), the XeF2 adduct-salts, [BrOF2][AsF 6]·nXeF2 (n = 1, 2), and the KrF2 adduct-salt, [BrOF2][AsF6]˙2KrF 2, are also described. The crystal structure of [BrOF2][AsF 6] shows a positional disorder among the oxygen atom and the fluorine atoms. The low-temperature Raman spectra of [XOF2][AsF6], the complex cation salts, [BrOF2][AsF6]· nXeF2 (n = 1,2), and [BrOF2][AsF 6]·2KrF2 have been assigned on the basis of the crystal structures and with the aid of quantum-chemical calculations.;The syntheses of FXeON16O2 and FXeONe( 18OO) has shed light on the mechanism leading to the formation of FXeONO2. Raman spectroscopy indicated the absence of 16/18 O isotopic scrambling among the oxygen sites of FXeONO2 which was confirmed by factor-group analyses of the 16 isotopomeric crystallographic unit cells that result from syn-/anti-isomerization, FXe 16ON(16OA18OS)/FXe 16ON(16OS18OA), among the four FXeONO2 molecules of the unit cell. The intermediate oxide fluoride, O(XeF)2, was observed in the synthesis of FXeONO2, providing valuable insight into the reaction pathway. (Abstract shortened by UMI.);The XeOF3- anion has been synthesized as its Cs+ and N(CH3)4+ salts, and structurally characterized in the solid state by low-temperature Raman spectroscopy. The calculated anion geometry is based on a square planar AX 3YE2 VSEPR arrangement with the longest Xe--F bond trans to the oxygen atom. The F--Xe--F angle is bent away from the oxygen atom to accommodate the greater spatial requirement of the oxygen double bond domain.
机译：该论文扩展了稀有气体元素氙和k的基本化学性质。更具体地说，Xe（IV）的化学性质已通过Xe（IV）氧化物和氧化物氟化物衍生物的合成和表征得到扩展。描述了XeOF 2，F 2 OXeN 3 CCH 3和XeOF2 nHF的合成及其结构表征。这三种化合物在接近0°C的温度下都具有吸热和爆炸性。尽管以前已经报道过XeOF2，但尚未分离出其为纯化合物。现在已经在CH 3 CN溶液中通过19 F，17 O和129 Xe NMR光谱和XeOF 2，F 2 OXeN 3 CCH 3和XeOF 2表征了二氟化氙。 nHF已通过拉曼光谱表征。; [H（OXeF2）n] [AsF6]和[FXeII（OXeIVF2）n] [AsF6]盐已经合成并进行了结构表征固态拉曼光谱仪每个阳离子的链长限制为一个或两个OXeF2亚基，它们是氧桥连的，并且与AsF6-阴离子强烈离子配对。 XeOF2-xHF在超酸性HF / SbF5溶剂混合物中的反应产生了[[XeF3＆HF] [Sb2F11]）2·[H 5F4] [SbF6]，[XeF3＆HF] [Sb 2F11]的混合物; [XOF2] [AsF 6]（X = Cl，Br），XeF2加合物盐，[BrOF2] [AsF 6]·nXeF2（n = 1）的合成和结构表征也描述了KrF 2加合物盐[BrOF 2] [AsF 6] 2 KrF 2。 [BrOF2] [AsF 6]的晶体结构显示氧原子和氟原子之间的位置无序。 [XOF2] [AsF6]，络合阳离子盐，[BrOF2] [AsF6]·nXeF2（n = 1,2）和[BrOF2] [AsF 6]·2KrF2的低温拉曼光谱已指定在FXeON16O2和FXeONe（18OO）的合成阐明了导致FXeONO2形成的机理。拉曼光谱表明FXeONO2的氧位点之间不存在16/18 O同位素加扰，这一点已通过对16个同位素异构体晶体学单元格的因子组分析进行了证实，该单元格是由于同位/反异构化，FXe 16ON（16OA18OS）/ FXe晶胞的四个FXeONO2分子中的16ON（16OS18OA）。在FXeONO2的合成中观察到了中间氧化物氟化物O（XeF）2，为反应途径提供了有价值的见解。 XeOF3-阴离子已作为其Cs +和N（CH3）4+盐合成，并通过低温拉曼光谱在固态下进行结构表征。计算得出的阴离子几何结构基于具有最长Xe-F键反式至氧原子的正方形平面AX 3YE2 VSEPR排列。 F–Xe–F角远离氧原子弯曲以适应氧双键域的更大空间要求。

著录项

  • 作者

    Brock, David S.;

  • 作者单位

    McMaster University (Canada).;

  • 授予单位 McMaster University (Canada).;
  • 学科 Chemistry Inorganic.
  • 学位 Ph.D.
  • 年度 2011
  • 页码 409 p.
  • 总页数 409
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

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