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 |
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| Authors: | Alejandro Portugués Dr Delia Bautista Dr Juan Gil-Rubio |
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| Institution: | 1. Departamento de Química Inorgánica, Facultad de Química, Universidad de Murcia, Campus de Espinardo, 30100 Murcia, Spain;2. ACTI, Universidad de Murcia, Campus de Espinardo, 30100 Murcia, Spain |
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| Abstract: | New dinuclear Au(I), Au(II) and Au(III) complexes containing (CF2)n bridging chains were obtained. Metallomacrocycles Au2{μ-(CF2)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(CF2)4AuL (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. |
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| Keywords: | aurophilicity fluorinated ligands gold metallacycles metal-metal interactions |
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