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

Abstract

In the absence of halides, anionic sulfur containing ligands generally produce multi nuclear products with CuI and AgI For example, CuII and AgI acetates react with mercaptothiazoline, HMT, to produce tetranuclear CuI and AgI clusters which polymerize, [Mn(MT)4]n. Tetranuclear dithiocarbamates, M4(DTC)4, and dithiophosphates, M4(DDP)4, are important commercial chemicals with Cu4(DDP)4 functioning as an important anti-oxidant in motor oils. CuI-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 CuI and AgI with 1,1-dithiol ligands. Clusters and cages such as [Cu6(S2P(OiPr)2)6] and {Cu8 [S2P(QiPr)2]6 S} are described along with their structural relationship to [Zn4(S2P(OEt)2)6S].