The one-electron oxidizing agent [NO]PF<sub>6</sub> was reacted with Bu<sub>4</sub>N[Au(C<sub>6</sub>X<sub>5</sub>)<sub>2</sub>] (X = F, Cl) complexes in CH<sub>3</sub>CN. The gold(III) complexes [Au(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>(CH<sub>3</sub>CN)] and <i>cis</i>-[Au(C<sub>6</sub>Cl<sub>5</sub>)<sub>2</sub>(CH<sub>3</sub>CN)<sub>2</sub>]PF<sub>6</sub> were synthesized by the oxidation of gold(I) to gold(III) with the concomitant ligand rearrangement “oxidative rearrangement”. The supramolecular crystal packing in the perfluorinated aryl gold(III) complex is dictated by the notably short C(sp<sup>2</sup>)–F···H(CH<sub>3</sub>CN) bond distance. The [Au(C<sub>6</sub>Cl<sub>5</sub>)<sub>2</sub>(CH<sub>3</sub>CN)<sub>2</sub>]PF<sub>6</sub> complex exhibits antisymbiosis, displaying equal ligands in the cis position. The electrochemical oxidation of Bu<sub>4</sub>N[Au(C<sub>6</sub>X<sub>5</sub>)<sub>2</sub>] (X = F, Cl) complexes in CH<sub>3</sub>CN showed two irreversible peaks at 0.71 and 1.21 V (X = F) and at 0.65 and 0.91 V (X = Cl) vs Ag/AgCl
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