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

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(CF 3 ) 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 [SbF 6 ] - 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 [P 9 ] + 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+ .