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

Abstract

AbstractThe perfluorinated dihydrophenazine derivative (perfluoro‐5,10‐bis(perfluorophenyl)‐5,10‐dihydrophenazine) (“phenazineF”) can be easily transformed to a stable and weighable radical cation salt by deelectronation (i.e. oxidation) with Ag[Al(ORF)4]/ Br2 mixtures (RF=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 [FeIIICp*2]+ to [FeIV(CO)Cp*2]2+ and [FeIV(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.