Mixed-valent gold (0,1) clusters have been synthesized from suitable oligonuclear gold(I) clusters, but advances in this area have been slowed by the difficulty in synthesizing convenient and versatile precursors. Cationic (N-heterocyclic carbene)gold(I) cation equivalents are prone to the formation of inert homoleptic cations of the type [L2Au]+ unless the supporting ligand is very bulky, in which case pyramidal precursors of the type [(LAu)3O]+, well known for other ligand types, fail to form. Softer Lewis bases such as sulfide overcome this difficulty, forming anion-bridged oligogold cations with no detectable homoleptic byproduct, but have proven quite difficult to reduce. We have turned to bridging halides, especially bromide, to strike a balance between binding tightly enough to suppress homoleptic cation formation, and binding too tightly to permit facile reduction. The reduction of complexes such as [(LAu)2Br]+, and related species, using both main group- and transition metal-based reductants, will be presented. It

Metal-metal bonds from halide-bridged group 11 metal cations

253rd National Meeting (2017)

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