Tetrahedral, octahedral, cubal and centered cubal dithiolate clusters and cages of Cu(I) and Ag(I)

In the absence of halides, anionic sulfur containing ligands generally produce multi nuclear products with Cu-I and Ag-I. For example, Cu-II and Ag-I acetates react with mercaptothiazoline, HMT, to produce tetranuclear Cu-I and Ag-I clusters which polymerize, [M-n(MT)(4)](n). Tetranuclear dithiocarbamates, M-4(DTC)(4), and dithiophosphates, M-4(DDP)(4), are important commercial chemicals with Cu-4(DDP)(4) functioning as an important anti-oxidant in motor oils. Cu-I-S clusters also have been implicated in biological redox chemistry. With the i-MNT ligand, hexa- and octanuclear complexes are also known. This paper summarizes the current knowledge of the synthesis and structural chemistry of Cu-I and Ag-I with 1,1-dithiol ligands. Clusters and cages such as [Cu-6(S2P((OPr)-Pr-i)(2))(6)] and {Cu-8[S2P((OPr)-Pr-i)(2)](6)S} are described along with their structural relationship to [Zn-4(S2P(OEt)(2))(6)S].