Abstract
The reaction of fumaryl fluoride with the superacidic solutions XF/MF5 (X=H, D;M=As, Sb) results in the formation of the monoprotonated and diprotonated species, dependent on the stoichiometric ratio of the Lewis acid to fumaryl fluoride. The salts [C4H3F2O2](+)[MF6](-) (M=As, Sb) and [C4H2X2F2O2](2+)([MF6](-))(2) (X=H, D;M=As, Sb) are the first examples with a protonated acyl fluoride moiety. They were characterized by low-temperature vibrational spectroscopy. Low-temperature NMR spectroscopy and single-crystal X-ray structure analyses were carried out for [C4H3F2O2](+)[SbF6](-) as well as for [C4H4F2O2](2+)([MF6](-))(2) (M=As, Sb). The experimental results are discussed together with quantum chemical calculations of the cations [C4H4F2O2 . 2 HF](2+) and [C4H3F2O2 . HF](+) at the B3LYP/aug-cc-pVTZ level of theory. In addition, electrostatic potential (ESP) maps combined with natural population analysis (NPA) charges were calculated in order to investigate the electron distribution and the charge-related properties of the diprotonated species. The C-F bond lengths in the protonated dication are considerably reduced on account of the +R effect.
Item Type: | Journal article |
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Faculties: | Chemistry and Pharmacy > Department of Chemistry |
Subjects: | 500 Science > 540 Chemistry |
URN: | urn:nbn:de:bvb:19-epub-106967-1 |
ISSN: | 0947-6539 |
Language: | English |
Item ID: | 106967 |
Date Deposited: | 11. Sep 2023, 13:45 |
Last Modified: | 09. Oct 2023, 18:17 |
DFG: | Gefördert durch die Deutsche Forschungsgemeinschaft (DFG) - 491502892 |