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Improved Access to Organo-Soluble Di- and Tetrafluoridochlorate(I)/(III) Salts

Pröhm , Patrick; Schmid, J. R.; Sonnenberg, K.; Voßnacker, P.; Steinhauer, S.; Schattenberg, Caspar Jonas; Müller, Robert; Kaupp, Martin; Riedel, Sebastian

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]−.
Published in: Angewandte Chemie, 10.1002/anie.202006268, Wiley