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 ") can be easily transformed to a stable and weighable radical cation salt by deelectronation (i.e. oxidation) with Ag[Al(OR ) ]/ Br mixtures (R =C(CF ) ). 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 C H ; E°'=1.29 V). It allows for the deelectronation of [Fe Cp* ] to [Fe (CO)Cp* ] and [Fe (CN- Bu)Cp* ] in common laboratory solvents and is compatible with good σ-donor ligands, such as L=trispyrazolylmethane, to generate novel [M(L) ] complex salts from the respective elemental metals.