Zwitterionic Metalates of Group 11 Elements and Their Use as Metalloligands for the Assembly of Multizwitterionic Clusters

Reaction of RNHC(S)PPh2NPPh2C(S)NR (HRSNS; R ) Me, Et) with MI (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-2 and S,N,S-3 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.