Synthesis and Stabilization of Highly Reactive Haloacetylium Ions
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.
Authors
- Alexander Nitzer (ORCID: https://orcid.org/0000-0003-4903-9603)
- Andreas Kornath (ORCID: https://orcid.org/0000-0002-7307-4516)
- Valentin Bockmair
- Sebastian Steiner (ORCID: https://orcid.org/0000-0002-5286-3567)
- Christoph Jessen
Institutions
- Ludwig-Maximilians-Universität München (DE)
Publication Details
- Journal
- The Journal of Organic Chemistry
- Published
- 2024-09-23
- DOI
- https://doi.org/10.1021/acs.joc.4c01783
- Citations
- 3
- Primary Topic
- Synthesis and Biological Evaluation
- Type
- article
- Field-Weighted Citation Impact
- 0.75
Funders
- Deutsche Forschungsgemeinschaft
- Fakultät für Chemie und Pharmazie, Ludwig-Maximilians-Universität München