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)]/ Br(2) mixtures (R(F)=C(CF(3))(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‐F(2)C(6)H(4); 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.