The Tris(pentafluorophenyl)methylium Cation: Isolation and Reactivity. Issue 28 (16th May 2022)

• Record Type: Journal Article
• Authors: Hoffmann, Kurt F.; Battke, David; Golz, Paul; Rupf, Susanne M.; Malischewski, Moritz; Riedel, Sebastian
• Is Part Of: Angewandte Chemie international edition. Volume 61:Issue 28(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-05-16
• Subjects: High Hydride Affinity -- Perfluorinated Trityl Cation -- Strong Oxidizer -- Superacids -- Weakly Coordinating Anions; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202203777
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Herein, we present two different routes for the synthesis of the perfluorinated trityl cation, which allowed the handling of the free, uncoordinated species in organic solvents for the first time. The usage of the weakly coordinating anion [Al(OTeF5 )4 ] − and its derivatives allows the characterization of this species by NMR spectroscopy and most importantly by single‐crystal X‐ray diffraction. The high hydride ion affinity of the cation is shown by hydrogen abstraction from isobutane. Furthermore, cyclic voltammetry reveals its oxidative potential which is supported by the reaction with tris(4‐bromophenyl)amine, giving rise to the formation of the ammoniumyl radical cation, also known as "magic blue". Abstract : Two brave knights worrying for their hydrides and electrons are caught in the storm of a small tritylium and a giant perfluorotritylium windmill. Herein, the structural proof of the perfluorinated trityl cation and its remarkable hydride ion affinity and oxidation potential compared to its non‐fluorinated analogue are reported.