Protonated oxalyl chloride and the ClCO⁺ cation.

IF 0.7 4区化学 Q4 CHEMISTRY, MULTIDISCIPLINARY

Acta Crystallographica Section C Structural Chemistry Pub Date : 2024-12-01 Epub Date: 2024-11-20 DOI:10.1107/S2053229624010714

Sebastian Steiner, Kristina Djordjevic, Valentin Bockmair, Dirk Hollenwäger, Andreas J Kornath

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Abstract

The reactions of oxalyl chloride were investigated in the binary superacidic systems HF/SbF₅ and DF/SbF₅. O-Monoprotonated oxalyl chloride was isolated and represents the first example of a protonated acyl chloride. Diprotonated oxalyl chloride is only stable in solution. Salts of the ClCO⁺ cation were synthesized from the reactions of oxalyl chloride or COClF with SbF₅ in 1,1,1,2-tetrafluoroethane (R-134a, CF₃CFH₂). The colourless salts were characterized by low-temperature vibrational spectroscopy, NMR spectroscopy and single-crystal X-ray diffraction. (1,2-Dichloro-2-oxoethylidene)oxidanium hexafluoridoantimonate(V), [C₂O(OH)Cl₂][SbF₆], crystallizes in the monoclinic space group P2₁ and carbonyl chloride hexadecafluoridotriarsenate(V) [ClCO][Sb₃F₁₆], in the trigonal space group P3₁, with two and three formula units per unit cell, respectively. Monoprotonated oxalyl chloride and the ClCO⁺ cation both display very short C-Cl bonds with a strong double-bond character.

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质子化草酰氯和 ClCO+ 阳离子。

研究了草酰氯在二元超酸性体系 HF/SbF5 和 DF/SbF5 中的反应。分离出了 O-单质子草酰氯，这是质子酰基氯的第一个实例。双质子草酰氯仅在溶液中稳定。草酰氯或 COClF 与 SbF5 在 1,1,1,2- 四氟乙烷（R-134a，CF3CFH2）中的反应合成了 ClCO+ 阳离子盐。低温振动光谱、核磁共振光谱和单晶 X 射线衍射对无色盐进行了表征。(1,2-Dichloro-2-oxoethylidene)oxidanium hexafluoridoantimonate(V)，[C2O(OH)Cl2][SbF6]，在单斜空间群 P21 中结晶；羰酰氯十六氟三胂酸盐(V)[ClCO][Sb3F16]，在三方空间群 P31 中结晶，每个单胞分别有两个和三个式单元。单质子草酰氯和 ClCO+ 阳离子都显示出非常短的 C-Cl 键，具有很强的双键特性。

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来源期刊

Acta Crystallographica Section C Structural Chemistry CHEMISTRY, MULTIDISCIPLINARYCRYSTALLOGRAPH-CRYSTALLOGRAPHY

CiteScore

1.60

自引率

12.50%

发文量

148

期刊介绍： Acta Crystallographica Section C: Structural Chemistry is continuing its transition to a journal that publishes exciting science with structural content, in particular, important results relating to the chemical sciences. Section C is the journal of choice for the rapid publication of articles that highlight interesting research facilitated by the determination, calculation or analysis of structures of any type, other than macromolecular structures. Articles that emphasize the science and the outcomes that were enabled by the study are particularly welcomed. Authors are encouraged to include mainstream science in their papers, thereby producing manuscripts that are substantial scientific well-rounded contributions that appeal to a broad community of readers and increase the profile of the authors.