Reaction of RNHC(S)PPh2NPPh2C(S)NR (HRSNS; R = Me, Et) with M(I) (M = Cu, Ag, Au) salts afforded zwitterionic complexes of the general formula [M(RSNS)] (M = Cu, Ag, Au). The ligand was found in the solid state in S,S-kappa2 and S,N,S-kappa3 coordination fashions. [Cu(RSNS)] and [Ag(RSNS)] can be used as metalloligand building blocks for the assembly of pentanuclear multizwitterionic Cu5, Cu3Ag2 and Ag5 core clusters of the general formula [M'2{M(RSNS)}3]2+ (M = Cu, M' = Cu, Ag; M = M' = Ag) upon reaction with suitable M' salts. The crystal structures of the most significant compounds are reported herein. Compound [Ag2{Ag(RSNS)}2(OTf)2] was also isolated and structurally characterized, representing a model for the intermediate species of the aforementioned assembly.