Oxidative Fluorination of Selenium and Tellurium Compounds using a Thermally Stable Phosphonium SF₅ ^- Salt Accessible...

Fluorinated group 16 moieties are attractive building blocks in synthetic chemistry but only few synthetic methods are available to prepare them. Herein, we report a new oxidative fluorination reagent capable of stabilizing reactive fluorinated anions. It consists of an SF₅ ^- anion and a chemically inert phosphonium cation and is exceptionally thermally stable. Accordingly, it was used to generate the SeF₅ ^- and TeF₅ ^- anions from the elemental chalcogens and to prepare the unknown tetrafluoro(phenyl)-λ⁵ -selenate PhSeF₄ ^- and -tellurate PhTeF₄ ^- from the corresponding diphenyl dichalcogenides. In addition, we show that further derivatization of [PhTeF₄ ]^- by oxidation to trans-PhTeF₄ O^- and subsequent alkylation gives access to a new class of trans-(alkoxy)(phenyl)tetrafluoro-λ⁶ -tellanes (trans-PhTeF₄ OR), thus providing an approach to introduce the functional group into organic molecules.