Sebastian Steiner, Christoph Jessen, Alexander Nitzer, Valentin Bockmair, Andreas J Kornath
{"title":"高活性卤乙酰离子的合成与稳定。","authors":"Sebastian Steiner, Christoph Jessen, Alexander Nitzer, Valentin Bockmair, Andreas J Kornath","doi":"10.1021/acs.joc.4c01783","DOIUrl":null,"url":null,"abstract":"<p><p>The reactions of selected haloacetyl fluorides with the strong Lewis acids AsF<sub>5</sub> and SbF<sub>5</sub> were investigated in the aprotic solvent SO<sub>2</sub>ClF. Depending on the stoichiometric ratio of AsF<sub>5</sub> or SbF<sub>5</sub> and the haloacetyl fluorides, either <i>O</i>-coordinated adducts or the respective haloacetylium ions were isolated as solids. The compounds were characterized by low-temperature vibrational spectroscopy and single-crystal X-ray diffraction. [CClH<sub>2</sub>CO][Sb<sub>2</sub>F<sub>11</sub>] and [CH<sub>2</sub>FCO][Sb<sub>2</sub>F<sub>11</sub>] crystallize in the monoclinic space group <i>P</i>2<sub>1</sub> with two formula units per unit cell. The reactivity of the haloacetyl fluorides under Lewis acidic conditions is discussed based on quantum chemical calculations of fluoride ion affinities on the BP/def2SVPP level of theory. The haloacetylium ions are stabilized in the solid-state phase by intermolecular C···F contacts and electron donation of the fluorine ligands of the anions as well as intramolecular hyperconjugation.</p>","PeriodicalId":57,"journal":{"name":"The Journal of Organic Chemistry","volume":null,"pages":null},"PeriodicalIF":3.3000,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Synthesis and Stabilization of Highly Reactive Haloacetylium Ions.\",\"authors\":\"Sebastian Steiner, Christoph Jessen, Alexander Nitzer, Valentin Bockmair, Andreas J Kornath\",\"doi\":\"10.1021/acs.joc.4c01783\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>The reactions of selected haloacetyl fluorides with the strong Lewis acids AsF<sub>5</sub> and SbF<sub>5</sub> were investigated in the aprotic solvent SO<sub>2</sub>ClF. Depending on the stoichiometric ratio of AsF<sub>5</sub> or SbF<sub>5</sub> and the haloacetyl fluorides, either <i>O</i>-coordinated adducts or the respective haloacetylium ions were isolated as solids. The compounds were characterized by low-temperature vibrational spectroscopy and single-crystal X-ray diffraction. [CClH<sub>2</sub>CO][Sb<sub>2</sub>F<sub>11</sub>] and [CH<sub>2</sub>FCO][Sb<sub>2</sub>F<sub>11</sub>] crystallize in the monoclinic space group <i>P</i>2<sub>1</sub> with two formula units per unit cell. The reactivity of the haloacetyl fluorides under Lewis acidic conditions is discussed based on quantum chemical calculations of fluoride ion affinities on the BP/def2SVPP level of theory. The haloacetylium ions are stabilized in the solid-state phase by intermolecular C···F contacts and electron donation of the fluorine ligands of the anions as well as intramolecular hyperconjugation.</p>\",\"PeriodicalId\":57,\"journal\":{\"name\":\"The Journal of Organic Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":3.3000,\"publicationDate\":\"2024-09-23\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"The Journal of Organic Chemistry\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.joc.4c01783\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, ORGANIC\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Organic Chemistry","FirstCategoryId":"1","ListUrlMain":"https://doi.org/10.1021/acs.joc.4c01783","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
Synthesis and Stabilization of Highly Reactive Haloacetylium Ions.
The reactions of selected haloacetyl fluorides with the strong Lewis acids AsF5 and SbF5 were investigated in the aprotic solvent SO2ClF. Depending on the stoichiometric ratio of AsF5 or SbF5 and the haloacetyl fluorides, either O-coordinated adducts or the respective haloacetylium ions were isolated as solids. The compounds were characterized by low-temperature vibrational spectroscopy and single-crystal X-ray diffraction. [CClH2CO][Sb2F11] and [CH2FCO][Sb2F11] crystallize in the monoclinic space group P21 with two formula units per unit cell. The reactivity of the haloacetyl fluorides under Lewis acidic conditions is discussed based on quantum chemical calculations of fluoride ion affinities on the BP/def2SVPP level of theory. The haloacetylium ions are stabilized in the solid-state phase by intermolecular C···F contacts and electron donation of the fluorine ligands of the anions as well as intramolecular hyperconjugation.
期刊介绍:
The Journal of Organic Chemistry welcomes original contributions of fundamental research in all branches of the theory and practice of organic chemistry. In selecting manuscripts for publication, the editors place emphasis on the quality and novelty of the work, as well as the breadth of interest to the organic chemistry community.