Investigation of Bis(Perfluoro‐tert‐Butoxy) Halogenates(I/III). Issue 70 (5th November 2021)

• Record Type: Journal Article
• Authors: Pröhm, Patrick; Berg, Willi R.; Rupf, Susanne M.; Voßnacker, Patrick; Riedel, Sebastian
• Is Part Of: Chemistry. Volume 27:Issue 70(2021)
• Page Start: 17676
• Page End: 17681
• Publication Date: 2021-11-05
• Subjects: computational chemistry -- fluorine chemistry -- halogen chemistry -- oxidation agents; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202103325
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: A systematic study of halogenate(I/III) anions with polyatomic ligands is presented. The bis(perfluoro‐ tert ‐butoxy) halogenates(I) [X(OC4 F9 )2 ] −, X=Cl, Br, I, of chlorine, bromine, and iodine are prepared as their tetraethylammonium salts and characterized with IR, Raman, and NMR spectroscopic methods, as well as single‐crystal X‐ray diffraction analyses. Spectroscopical data are supported by quantum‐chemical calculations. Additionally, the bonding situation of the species in question are analyzed and discussed. Furthermore, the oxidation to the corresponding halogenate(III) derivatives was studied. For [Br(OC4 F9 )2 ] −, oxidation with elemental fluorine gave [BrF2 (OC4 F9 )2 ] − . Iodide was directly oxidized by ClOC4 F9 to the I III species [I(OC4 F9 )4 ] −, which is a surprisingly inert anion that might be used as a weakly coordinating anion (WCA) in the future. For [Cl(OC4 F9 )2 ] −, the decomposition products of the synthetic approaches towards a chlorine(III) system were analyzed. Abstract : Chemistry with halogens in positive oxidation states, especially the lighter halogens, is challenging due to their high oxidation potential. An ensemble of halogen +I and +III compounds with a comparatively large ligand system was synthesized and characterized with experimental and quantum‐chemical methods. This study is envisioned as an example for the diverse but sometimes overlooked chemistry of group 17.