Utilizing the Perfluoronaphthalene Radical Cation as a Selective Deelectronator to Access a Variety of Strongly Oxidizing Reactive Cations

Abstract

AbstractA selective deelectronation reagent with very high potential of +2.00 (solution)/+2.41 V (solid‐state) vs. Fc+/0 and based on a room temperature stable perfluoronaphthalene (naphthaleneF) radical cation salt was developed and applied. The solid‐state deelectronation of commercial naphthaleneF with [NO]+[F{Al(ORF)3}2]− generates [naphthaleneF]+⋅[F{Al(ORF)3}2]− (ORF=OC(CF3)3) in gram scale. Thermochemical analysis unravels the solid‐state deelectronation potential of the starting [NO]+‐reagent to be +2.34 V vs. Fc+/0 with [F{Al(ORF)3}2]− counterion, but only +1.14 V vs. Fc+/0 with the small [SbF6]− ion. Selective reactions demonstrate the selectivity of [naphthaleneF]+⋅ for deelectronation of a multitude of organ(ometall)ic molecules and elements in solution: providing the molecular structures of the acene dications [tetracene]2+, [pentacene]2+ or spectroscopic evidence for the carbonyl complex of the ferrocene dication [Fc(CO)]2+, the [P9]+ cation from white phosphorus, the solvent‐free copper(I) salt starting from copper metal and the dicationic Fe(IV)‐scorpionate complex [Fe(sc)2]2+.