Structural investigations of benzoyl fluoride and the benzoacyl cation of low-melting compounds and reactive intermediates

Bockmair, Valentin ; Regnat, Martin; Tran, Huu Khanh Trinh und Kornath, Andreas J. (2025): Structural investigations of benzoyl fluoride and the benzoacyl cation of low-melting compounds and reactive intermediates. In: Acta Crystallographica Section C Structural Chemistry, Bd. 81, Nr. 2: S. 93-101

Abstract

Acyl fluorides and acyl cations represent typical reactive inter­mediates in organic reactions, such as Friedel–Crafts acyl­ation. However, the com­paratively stable phenyl-substituted com­pounds have not been fully characterized yet, offering a promising backbone. Attempts to isolate the benzo­acyl­ium cation have only been carried out starting from the acyl chloride with weaker chloride-based Lewis acids. Therefore, only adducts of 1,4-stabilized acyl cations could be obtained. Due to the low melting point of benzoyl fluoride, together with its volitality and sensitivity toward hydrolysis, the structures of the acyl fluoride and its acyl­ium cation have not been determined. Herein, we report the first crystal structure of benzoyl fluoride, C7H5FO or PhCOF (monoclinic P21/n, Z = 8) and the benzo­acyl­ium undeca­fluoro­diarsenate, C7H5O+·As2F11− or [PhCO]+[As2F11]− (monoclinic P21/n, Z = 4). The com­pounds were characterized by low-tem­per­a­ture vibrational spectroscopy and single-crystal X-ray analysis, and are discussed together with quantum chemical calculations. In addition, their specific π-inter­actions were elucidated.

• Dokumententyp: Zeitschriftenartikel
• Fakultät: Chemie und Pharmazie > Department Chemie
• Themengebiete: 500 Naturwissenschaften und Mathematik > 540 Chemie
• ISSN: 2053-2296
• Sprache: Englisch
• DFG: Gefördert durch die Deutsche Forschungsgemeinschaft (DFG) - 513247541