Use of the CH Acidity of 2,4,4-Trimethyl-4,5-dihydrooxazole to Synthesize Triauriomethanes and Novel Gold Clusters

An Au 8I cluster with an unusual structure, the dication 1, is formed in the polyauration of 2,4,4‐trimethyl‐4,5‐dihydrooxazole. The expected dihydrooxazole with a peraurated 2‐methyl group reacts further with excess Ph3PAuCl/CsF under Au1‐incorporation to give 1. The highly aurated C atoms are trigonal‐bipyramidally coordinated. Since the distance between the two central Au atoms is also short (2.811(1) (Å), all the eight Au atoms are components of a cluster. The counterion [Me3SiF2]⊖ was also unexpected.