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

Abstract

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.

Cations and Anions of Dibenzo[a,e]pentalene and Reduction of a Dibenzo[a,e]pentalenophane

“…For the oxidation of 1 a strong yet innocent oxidant, facilitating an outer‐sphere electron transfer, was required. Based on its high oxidation potential (see above), we used the perfluorinated dihydrophenazine cation radical of salt 3 , which was recently introduced as a strong oxidant [38] …”

“…Based on its high oxidation potential (see above), we used the perfluorinated dihydrophenazine cation radicalo fs alt 3,w hich was recently introduced as as trong oxidant. [38] Its formal reduction potential lies at 1.29 Vv ersus Fc/Fc + in ortho-difluorobenzene( o-DFB), hence sufficiently high to oxidize 1 to ad ication. Thel arge Al-based weakly coordinating counterion Al(OR F ) 4 ] À (R F = C(CF 3 ) 3 ) [39] serves to stabilize generated reactive cationic species.…”

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

“…For the molecular structures of S1, S2, S3, and S4 see Supporting Information. [28] Angewandte Chemie Forschungsartikel generated and is stable in both oDFB and CH 2 Cl 2 as solvent. In analogy to the described procedure, the respective [SbF 6 ] À salt can be accessed, when employing Ag[SbF 6 ] in SO 2 solution giving stable deeply purple colored solutions.…”

“…Thermal displacement ellipsoids set at 50 % probability. [28] Some selected spectroscopic data is included.…”

“…Data collected at 100 K. Cocrystallized CH 2 Cl 2 omitted for clarity. Thermal displacement ellipsoids set at 50 % probability [28]. c) Cyclic voltammogram of 3 (10 mm) in MeCN with Fc + /Fc as internal reference and [NBu 4 ][Al(OR F ) 4 ] (100 mm) as conducting salt.…”