The bis(metallaethynyl) ketone {(Ph₃P)AuC≡C}₂CO (1), obtained from (Me₃SiC≡C)₂CO, AuCl(PPh₃), and NaOMe, forms an Au•••Au-bonded dimer in the solid state (Au•••Au = 2.9825(3) Å). The ES-MS contains ions [2M + X]⁺ (X = Na, K, Au), but the lack of the ion [2M]⁺ and NMR evidence suggest that the dimeric structure is not preserved in solution. Compound 1 reacts with RuCl(dppe)Cp to afford the unusual dimetal-substituted pyrylium complex [1,3-{Ru(dppe)Cp}₂{c-COC(OMe)CHCCH}]PF₆ (2). The molecular structure of 2 is also reported, together with a proposed route for its formation.