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 isolate...
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| Published in: | Journal of organic chemistry Vol. 89; no. 19; pp. 14399 - 14407 |
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| Main Authors: | , , , , |
| Format: | Journal Article |
| Language: | English |
| Published: |
United States
American Chemical Society
04-10-2024
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| Online Access: | Get full text |
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| Summary: | 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. |
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| Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
| ISSN: | 0022-3263 1520-6904 1520-6904 |
| DOI: | 10.1021/acs.joc.4c01783 |