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 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-κ² and S,N,S-κ³ 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.