Galvanic replacement-induced introduction of a heteroligand into bimetallic and trimetallic nanoclusters.

Heteroleptic 8-electron silver-rich alloy nanoclusters, [Au@Au 4 Ag 12 (dtp) 7 (PPh 3 ) 4 ] 2+ (1) and [Pt@Au 4 Ag 11 (dtp) 7 (PPh 3 ) 4 ] (2), were successfully synthesized via a galvanic replacement reaction of 1,1-dithiolate-protected M@Ag 20 (M = Au and Pt) nanoclusters with Au(I)-phosphine salts, leading to the alteration of the cluster nuclearity and geometry of shell skeletons but retaining the same 8-electron count.