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 AgAl(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‐F₂C₆H₄; E°′=1.29 V). It allows for the deelectronation of Fe^IIICp*₂]⁺ to Fe^IV(CO)Cp*₂]²⁺ and Fe^IV(CN‐^tBu)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.