Sebastian Steiner, Kristina Djordjevic, Valentin Bockmair, Dirk Hollenwäger, Andreas J Kornath
{"title":"质子化草酰氯和 ClCO+ 阳离子。","authors":"Sebastian Steiner, Kristina Djordjevic, Valentin Bockmair, Dirk Hollenwäger, Andreas J Kornath","doi":"10.1107/S2053229624010714","DOIUrl":null,"url":null,"abstract":"<p><p>The reactions of oxalyl chloride were investigated in the binary superacidic systems HF/SbF<sub>5</sub> and DF/SbF<sub>5</sub>. 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<sup>+</sup> cation were synthesized from the reactions of oxalyl chloride or COClF with SbF<sub>5</sub> in 1,1,1,2-tetrafluoroethane (R-134a, CF<sub>3</sub>CFH<sub>2</sub>). 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), [C<sub>2</sub>O(OH)Cl<sub>2</sub>][SbF<sub>6</sub>], crystallizes in the monoclinic space group P2<sub>1</sub> and carbonyl chloride hexadecafluoridotriarsenate(V) [ClCO][Sb<sub>3</sub>F<sub>16</sub>], in the trigonal space group P3<sub>1</sub>, with two and three formula units per unit cell, respectively. Monoprotonated oxalyl chloride and the ClCO<sup>+</sup> cation both display very short C-Cl bonds with a strong double-bond character.</p>","PeriodicalId":7115,"journal":{"name":"Acta Crystallographica Section C Structural Chemistry","volume":" ","pages":"792-797"},"PeriodicalIF":0.7000,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11619778/pdf/","citationCount":"0","resultStr":"{\"title\":\"Protonated oxalyl chloride and the ClCO<sup>+</sup> cation.\",\"authors\":\"Sebastian Steiner, Kristina Djordjevic, Valentin Bockmair, Dirk Hollenwäger, Andreas J Kornath\",\"doi\":\"10.1107/S2053229624010714\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>The reactions of oxalyl chloride were investigated in the binary superacidic systems HF/SbF<sub>5</sub> and DF/SbF<sub>5</sub>. 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<sup>+</sup> cation were synthesized from the reactions of oxalyl chloride or COClF with SbF<sub>5</sub> in 1,1,1,2-tetrafluoroethane (R-134a, CF<sub>3</sub>CFH<sub>2</sub>). 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), [C<sub>2</sub>O(OH)Cl<sub>2</sub>][SbF<sub>6</sub>], crystallizes in the monoclinic space group P2<sub>1</sub> and carbonyl chloride hexadecafluoridotriarsenate(V) [ClCO][Sb<sub>3</sub>F<sub>16</sub>], in the trigonal space group P3<sub>1</sub>, with two and three formula units per unit cell, respectively. Monoprotonated oxalyl chloride and the ClCO<sup>+</sup> cation both display very short C-Cl bonds with a strong double-bond character.</p>\",\"PeriodicalId\":7115,\"journal\":{\"name\":\"Acta Crystallographica Section C Structural Chemistry\",\"volume\":\" \",\"pages\":\"792-797\"},\"PeriodicalIF\":0.7000,\"publicationDate\":\"2024-12-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11619778/pdf/\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Acta Crystallographica Section C Structural Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1107/S2053229624010714\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2024/11/20 0:00:00\",\"PubModel\":\"Epub\",\"JCR\":\"Q4\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Acta Crystallographica Section C Structural Chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1107/S2053229624010714","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2024/11/20 0:00:00","PubModel":"Epub","JCR":"Q4","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
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.
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.
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