Dinuclear Au(I), Au(II) and Au(III) Complexes with (CF ) 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 ) bridging chains were obtained. Metallomacrocycles [Au {μ-(CF ) }{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 ) AuL (L=PPh , PMe , (dppf) , (binap) ) gave [Au(II)] species, some of which display unprecedented folded structures with Au-Au bonds. Aurophilic interactions facilitate this oxidation process by preorganizing the starting [Au(I)] complexes and lowering its redox potential. The obtained [Au(II)] complexes undergo thermal or photochemical elimination of R PAuX to give Au(III) perfluorinated auracycles. Evidence of a radical mechanism for these decomposition reactions was obtained.