The 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.

Supporting information (experimental details, procedures, weights, 1D-and 2D-NMR spectra, IR spectra and powder diffraction patterns of the reactions, details to the quantum chemical calculations and crystallographic details) and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Radical Ions The synthesis and application of a perfluorinated phenazine ammoniumyl radical cation is presented by I. Krossing et al. in their Research Article on page 9453. This novel species provides access to tetravalent dicationic iron complexes in common laboratory solvents.

Radikalionen Die Synthese und Anwendung eines perfluorierten Phenazinammoniumyl‐Radikalanions wird von I. Krossing et al. im Forschungsartikel auf S. 9540 vorgestellt. Diese neuartige Spezies ermöglicht den Zugang zu vierwertigen dikationischen Eisenkomplexen in üblichen Lösungsmitteln.