Dinuclear Au(I), Au(II) and Au(III) Complexes with (CF2)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 (CF2)(n) bridging chains were obtained. Metallomacrocycles [Au-2{mu-(CF2)(4)}{mu-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(CF2)(4)AuL (L=PPh3, PMe3, (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 R3PAuX to give Au(III) perfluorinated auracycles. Evidence of a radical mechanism for these decomposition reactions was obtained.

Automated summary

New dinuclear gold complexes with fluoroalkyl bridging chains were synthesized, and the aurophilic interactions were found to play a crucial role in the complex structures and oxidation reactions. The study extends the understanding and synthesis possibilities of gold complexes.