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)l (M = Cu, Ag, Au). The ligand was found in the solid state in S,S-kappa(2) and S,N,S-kappa(3) coordination fashions. [Cu(RSNS)] and [Ag(RSNS)] can be used as metalloligand building blocks for the assembly of pentanuclear multizwitterionic Cu-5, Cu3Ag2 and Ag-5 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 [Ag-2{Ag(RSNS)}(2)(OTf)(2)] was also isolated and structurally characterized, representing a model for the intermediate species of the aforementioned assembly.