{Reference Type}: Journal Article
{Title}: Utilizing the Perfluoronaphthalene Radical Cation as a Selective Deelectronator to Access a Variety of Strongly Oxidizing Reactive Cations.
{Author}: Sellin M;Willrett J;Röhner D;Heizmann T;Fischer J;Seiler M;Holzmann C;Engesser TA;Radtke V;Krossing I;
{Journal}: Angew Chem Int Ed Engl
{Volume}: 63
{Issue}: 34
{Year}: 2024 Aug 19
{Factor}: 16.823
{DOI}: 10.1002/anie.202406742
{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 (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+.