Synthesis and Application of a Perfluorinated Ammoniumyl Radical Cation as a Very Strong Deelectronator

The perfluorinated dihydrophenazine derivative (perfluoro-5,10-bis(perfluorophenyl)-5,10-dihydrophenazine) ("phenazine^F ") can be easily transformed to a stable and weighable radical cation salt by deelectronation (i.e. oxidation) with Ag[Al(OR^F )₄ ]/ Br₂ mixtures (R^F =C(CF₃ )₃ ). As an innocent deelectronator it has a strong and fully reversible half-wave potential versus Fc⁺ /Fc in the coordinating solvent MeCN (E°'=1.21 V), but also in almost non-coordinating oDFB (=1,2-F₂ C₆ H₄ ; E°'=1.29 V). It allows for the deelectronation of [Fe^III Cp*₂ ]⁺ to [Fe^IV (CO)Cp*₂ ]²⁺ and [Fe^IV (CN-^t Bu)Cp*₂ ]²⁺ in common laboratory solvents and is compatible with good σ-donor ligands, such as L=trispyrazolylmethane, to generate novel [M(L)_x ]ⁿ⁺ complex salts from the respective elemental metals.