{"title":"Unexpected reaction of antimony pentafluoride with a fluorinated propellane","authors":"Matthias Bremer","doi":"10.1016/j.jfluchem.2024.110281","DOIUrl":null,"url":null,"abstract":"<div><p>While 1,3-dehydro-5,7-difluoroadamantane <strong>11</strong> reacts with SbF<sub>5</sub> in super acid media (SO<sub>2</sub>ClF) to generate the 1,3-dehydroadamant-5,7-diyl dication <strong>1</strong>, 1,3-dehydro-5-fluoroadamantane <strong>12</strong> fails to react analogously to produce the 1,3-dehydroadamant-5-yl cation <strong>9</strong>; instead, the 3,5-difluoro-1-adamantylcation <strong>13</strong> is formed. We present a computational study that explains this surprising behavior by the initial addition of Sb<sub>2</sub>F<sub>10</sub> to the propellane bond present in <strong>12</strong>. This is computed to be highly exothermic and leads to a zwitterionic (or ion-pair) species, which in turn reacts autocatalytically with HF to produce the observed fluorinated cation <strong>13</strong>, SbF<sub>3</sub>, and SbF<sub>6</sub><sup>–</sup>.</p></div>","PeriodicalId":357,"journal":{"name":"Journal of Fluorine Chemistry","volume":null,"pages":null},"PeriodicalIF":1.7000,"publicationDate":"2024-04-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0022113924000411/pdfft?md5=14094f767e6d9d02c80729ea51095d21&pid=1-s2.0-S0022113924000411-main.pdf","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Fluorine Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0022113924000411","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
While 1,3-dehydro-5,7-difluoroadamantane 11 reacts with SbF5 in super acid media (SO2ClF) to generate the 1,3-dehydroadamant-5,7-diyl dication 1, 1,3-dehydro-5-fluoroadamantane 12 fails to react analogously to produce the 1,3-dehydroadamant-5-yl cation 9; instead, the 3,5-difluoro-1-adamantylcation 13 is formed. We present a computational study that explains this surprising behavior by the initial addition of Sb2F10 to the propellane bond present in 12. This is computed to be highly exothermic and leads to a zwitterionic (or ion-pair) species, which in turn reacts autocatalytically with HF to produce the observed fluorinated cation 13, SbF3, and SbF6–.
期刊介绍：
The Journal of Fluorine Chemistry contains reviews, original papers and short communications. The journal covers all aspects of pure and applied research on the chemistry as well as on the applications of fluorine, and of compounds or materials where fluorine exercises significant effects. This can include all chemistry research areas (inorganic, organic, organometallic, macromolecular and physical chemistry) but also includes papers on biological/biochemical related aspects of Fluorine chemistry as well as medicinal, agrochemical and pharmacological research. The Journal of Fluorine Chemistry also publishes environmental and industrial papers dealing with aspects of Fluorine chemistry on energy and material sciences. Preparative and physico-chemical investigations as well as theoretical, structural and mechanistic aspects are covered. The Journal, however, does not accept work of purely routine nature.
For reviews and special issues on particular topics of fluorine chemistry or from selected symposia, please contact the Regional Editors for further details.
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