Dinuclear Au(I), Au(II) and Au(III) Complexes with (CF(2))(n) Chains: Insights into The Role of Aurophilic Interactions in the Au(I) Oxidation

New dinuclear Au(I), Au(II) and Au(III) complexes containing (CF(2))(n) bridging chains were obtained. Metallomacrocycles [Au(2){μ‐(CF(2))(4)}{μ‐diphosphine}] show an uncommon figure‐eight structure, the helicity inversion barrier of which is influenced by aurophilic interactions and steric constraints imposed by the diphosphine. Halogenation of LAu(CF(2))(4)AuL (L=PPh(3), PMe(3), (dppf)(1/2), (binap)(1/2)) gave [Au(II)](2) species, some of which display unprecedented folded structures with Au−Au bonds. Aurophilic interactions facilitate this oxidation process by preorganizing the starting [Au(I)](2) complexes and lowering its redox potential. The obtained [Au(II)](2) complexes undergo thermal or photochemical elimination of R(3)PAuX to give Au(III) perfluorinated auracycles. Evidence of a radical mechanism for these decomposition reactions was obtained.