Transmetalation of the potassium methanide complex, K{CH(PPh 2NSiMe3)2}, with [(Ph3P) 2Cul] afforded the corresponding copper complex [{CH(PPh 2NSiMe3)2}CuPPh3] (1), whereas the reaction of K{CH(PPh2NSiMe3)2} with [Ph 3PAuCl] resulted in the dinuclear gold complex [(Ph 3PAu)2{C(PPh2NSiMe3)2}] (2). The solid-state structure of 1 shows the formation of a six-membered metallacycle (N1-P1-C1-P2-N2-Cu) that has a twist boat conformation. In contrast, compound 2 is an α,α-diaurated species, in which the two gold atoms are coordinated in a linear fashion onto the ligand backbone. Photoluminescence measurements show that the latter compound has a strong violet emission. © 2006 American Chemical Society.