二氯乙酰氟在超酸性介质中的反应

Sebastian Steiner, Alexander Nitzer, Christoph Jessen, Andreas J. Kornath
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引用次数: 0

摘要

研究了二氯乙酰氟在超酸性物质 HF/MF5 和 DF/MF5 (M = As、Sb)中的情况。在二元超酸性体系 HF/MF5 和 DF/MF5(M = As、Sb)中,二氯乙酰氟的 O-半质子化物种以六氟砷酸盐和六氟锑酸盐的形式形成。在超酸性体系 XF/SbF5(X = H、D)中,过量的强路易斯酸 SbF5 与二氯乙酰氟发生反应,在 HF 或 DF 加成后分别生成羰基盐 [CCl2HCF2OX2][SbF6]。低温振动光谱、核磁共振光谱和单晶 X 射线衍射对这些无色盐进行了表征。[CCl2HC(OH)F][(CCl2HCOF)2H][SbF6][Sb2F11]和[CCl2HCF2OH2][SbF6]分别在单斜空间群 P21/c 和 P21/m 中结晶,每个单胞有两个公式单元。羰基鎓盐的晶体结构显示出很强的 O(-H)--F 氢键和很强的 F-F 相互作用。实验数据与在ωB97XD/aug-cc-pVTZ 理论水平上进行的量子化学计算一起进行了讨论。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Reactions of Dichloroacetyl Fluoride in Superacidic Media
Dichloroacetyl fluoride was investigated in the superacids HF/MF5 and DF/MF5 (M = As, Sb). The O-hemiprotonated species of dichloroacetyl fluoride is formed in the binary superacidic systems HF/MF5 and DF/MF5 (M = As, Sb) as hexafluoridoarsenates and hexafluoridoantimonates. With an excess of the strong Lewis acid SbF5 dichloroacetyl fluoride reacts under the formation of the oxonium salt [CCl2HCF2OX2][SbF6] in the superacidic system XF/SbF5 (X = H, D) after HF- or DF-addition, respectively. The colorless salts were characterized by low-temperature vibrational spectroscopy, NMR spectroscopy, and single-crystal X-ray diffraction. [CCl2HC(OH)F][(CCl2HCOF)2H][SbF6][Sb2F11] and [CCl2HCF2OH2][SbF6] crystallize in the monoclinic space groups P21/c and P21/m, respectively, with two formula units per unit cell each. The crystal structure of the oxonium salt shows strong O(-H)···F hydrogen bonds and strong F···F interactions. The experimental data are discussed together with quantum chemical calculations at the ωB97XD/aug-cc-pVTZ-level of theory.
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