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(ORF)(4)]/ Br-2 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 degrees '=1.21 V), but also in almost non-coordinating oDFB (=1,2-F2C6H4; E degrees '=1.29 V). It allows for the deelectronation of [(FeCp)-Cp-III*(2)](+) to [Fe-IV(CO)Cp*(2)](2+) and [Fe-IV(CN-Bu-t)Cp*(2)](2+) in common laboratory solvents and is compatible with good sigma-donor ligands, such as L=trispyrazolylmethane, to generate novel [M(L)(x)](n+) complex salts from the respective elemental metals.