Improved Access to Organo‐Soluble Di‐ and Tetrafluoridochlorate(I)/(III) Salts
Open Access
- 27 May 2020
- journal article
- research article
- Published by Wiley in Angewandte Chemie International Edition
- Vol. 59 (37) , 16002-16006
Abstract
A facile one‐pot gram‐scale synthesis of tetraalkylammonium tetrafluoridochlorate(III) [cat][ClF4] ([cat]=[NEt3Me]+, [NEt4]+) is described. An acetonitrile solution of the corresponding alkylammonium chloride salt is fluorinated with diluted fluorine at low temperatures. The reaction proceeds via the [ClF2]− anion which is structurally characterized for the first time. The potential application of [ClF4]− salts as fluorinating agents is evaluated by the reaction with diphenyl disulfide, Ph2S2, to pentafluorosulfanyl benzene, PhSF5. The CN moieties in acetonitrile and [B(CN)4]− are transferred in CF3 groups. Exposure of carbon monoxide, CO, leads to the formation of carbonyl fluoride, COF2, and elemental gold is dissolved under the formation of tetrafluoridoaurate [AuF4]−.Keywords
Funding Information
- Deutsche Forschungsgemeinschaft (387284271, SPP 1708)
This publication has 53 references indexed in Scilit:
- Discovery of practical production processes for arylsulfur pentafluorides and their higher homologues, bis- and tris(sulfur pentafluorides): Beginning of a new era of “super-trifluoromethyl” arene chemistry and its industryBeilstein Journal of Organic Chemistry, 2012
- One step synthesis of 1,1,1,4,4,4-hexafluorobutane from succinonitrileJournal of Fluorine Chemistry, 1999
- Preparation and vibrational spectra of N(CH3)4+IF2− and electronic structure calculations of IF2−, BrF2−, ClF2−, XeF2 and KrF2Journal of Fluorine Chemistry, 1998
- The Surprising Crystal Packing of ChlorinefluorideAngewandte Chemie International Edition, 1997
- Syntheses, properties, and structures of anhydrous tetramethylammonium fluoride and its 1:1 adduct with trans-3-amino-2-butenenitrileJournal of the American Chemical Society, 1990
- Explosive reactions of liquid mixtures of chlorine trifluoride with hydrocarbons and halocarbonsJournal of Fluorine Chemistry, 1986
- Fluorierungen organischer Verbindungen mit Chlortrifluorid, I. Einwirkung von Chlortrifluorid auf Benzol in der GasphaseEuropean Journal of Inorganic Chemistry, 1965
- Preparation of Nitrosyl TetrafluorochlorateJournal of the American Chemical Society, 1964
- Solvolysis Reactions in Chlorine Trifluoride and Bromine Pentafluoride: Preparation of the Tetrafluorochlorates and Hexafluorobromates of Potassium, Rubidium, and CesiumJournal of the American Chemical Society, 1964
- TETRAFLUOROHALATES OF CESIUM, RUBIDIUM AND POTASSIUM1Journal of the American Chemical Society, 1961