Facile Formation of Homoleptic Au(III) Trications via Simultaneous Oxidation and Ligand Delivery from [PhI(pyridine)2]2+

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Corbo, R., Pell, T. P., Stringer, B. D., Hogan, C. F., Wilson, D. J., Barnard, P. J., & Dutton, J. L. (2014). Facile formation of homoleptic Au(III) trications via simultaneous oxidation and ligand delivery from [PhI(pyridine)2]2+. Journal of the American Chemical Society, 136(35), 12415-12421. doi:10.1021/ja506365m



030701 Quantum Chemistry

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We report the first examples of Au(III) tricationic complexes bound only by neutral monodentate ligands, which are a new class of gold reagents. Oxidative addition to the bis-pyridine Au(I) cation, [Au(4-DMAP)2]+, using a series of dicationic I(III) oxidants of the general form [PhI(L)2]2+ (L = pyridine, 4-DMAP, 4-cyanopyridine) allows ready access to homoleptic and pseudo-homoleptic Au(III) complexes [Au(4-DMAP)2(L)2]3+. The facile oxidative addition of Au(I) species additionally demonstrates the efficacy of PhI(L)2]2+ reagents as halide-free oxidants for Au(I). Comparisons are made via attempts to oxidize NHC-Au(I)Cl, where introduction of the chloride anion results in complex mixtures via ligand and chloride exchange, demonstrating the advantage of using the pyridine-based homoleptic compounds. The new Au(III) trications show intriguing reactivity with water, yielding dinuclear oxo-bridged and rare terminal Au(III)−OH complexes.


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At the time of writing David Wilson was affiliated with Avondale College as a Conjoint Lecturer.