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

Abstract

A 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 (naphthalene^F) radical cation salt was developed and applied. The solid-state deelectronation of commercial naphthalene^F with [NO]⁺[F{Al(OR^F)₃}₂]^- generates [naphthalene^F]⁺⋅[F{Al(OR^F)₃}₂]^- (OR^F=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(OR^F)₃}₂]^- counterion, but only +1.14 V vs. Fc^+/0 with the small [SbF₆]^- ion. Selective reactions demonstrate the selectivity of [naphthalene^F]⁺⋅ 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⁺.