Synthesis and Application of a Perfluorinated Ammoniumyl Radical Cation as a Very Strong Deelectronator
Marcel Schorpp, Tim Heizmann, Maximillian Schmucker, Stephan Rein, Stefan Weber, Ingo Krossing
Abstract
Abstract 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(OR F ) 4 ]/ Br 2 mixtures (R F =C(CF 3 ) 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 o DFB (=1,2‐F 2 C 6 H 4 ; E °′=1.29 V). It allows for the deelectronation of [Fe III Cp* 2 ] + to [Fe IV (CO)Cp* 2 ] 2+ and [Fe IV (CN‐ t Bu)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.