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• 作者：Hermann-Josef Frohn ; Vural Bilir ; Ulrich Westphal
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：November 5, 2012
• 年：2012
• 卷：51
• 期：21
• 页码：11251-11258
• 全文大小：305K
• 年卷期：v.51,no.21(November 5, 2012)
• ISSN：1520-510X

文摘

In the 1:1 reaction of XeF₂ with 1,4-(F₂B)₂C₆F₄ in 1,1,1,3,3-pentafluoropropane the insoluble zwitterion 2,3,5,6-tetrafluorophenylene-1-xenonium-4-trifluoroborate, 1-(Xe⁺)C₆F₄-4-(BF₃^{鈥?/sup>), was formed as the main product (77%) along with the zwitterion, 1-(Xe+)-cyclo-1,4-C₆F₆-4-(BF₃鈥?/sup>), the [BF₄]鈭?/sup> salts of the dication, [1,4-(Xe)₂C₆F₄]2+, and the cation, [1-Xe-cyclo-1,4-C₆F₆-4-H]+. The isolation of pure 1-(Xe+)C₆F₄-4-(BF₃鈥?/sup>) was feasible after extraction of the byproduct with 27% aq HF. The zwitterion, 1-(Xe+)C₆F₄-4-(BF₃鈥?/sup>), was characterized by multi-NMR and Raman spectroscopy and by DSC. The zwitterion, 1-(Xe+)C₆F₄-4-(BF₃鈥?/sup>), reacted with halide nucleophiles (in excess) in 27% aq HF to form [4-HalC₆F₄BF₃]鈭?/sup> (Hal = I, Br, Cl) along with [2,3,5,6-C₆F₄HBF₃]鈭?/sup>, whereas with fluoride ions [2,3,5,6-C₆F₄HBF₃]鈭?/sup> was obtained exclusively. Reactions of XeF₂ with 1,4-(F₂B)₂C₆F₄ in the molar ratio 2:1 did not allow for improving the yield of the tetrafluoroborate salt with the dication [1,4-(Xe)₂C₆F₄]2+. Instead, addition of fluorine to the phenylene unit was increased with the formation of 1-(Xe+)-cyclo-1,4-C₆F₆-4-(BF₃鈥?/sup>), [1-Xe-cyclo-1,4-C₆F₆-4-H]+, and [1,4-(Xe)₂-cyclo-1,4-C₆F₆]2+. After enrichment in an anhydrous hydrogen fluoride extract, the dication, [1,4-(Xe)₂C₆F₄]2+, was characterized by multi-NMR spectroscopy and by means of chemical proof (reaction with an excess of KI to 1,4-I₂C₆F₄).}