Reaction of S2CC(PPh3)2 with Silver Salts Containing Weakly Coordinating Anions; Preparation and Crystal Structures of [Ag6{S2CC(PPh3)2}4][BF4]6 · 9.75CH2CL2 and [Ag4{S2CC(PPh3)2}4][Al{OC(CF3)3}4]4 · 4.25C2H4Cl2

The betain-like carbodiphosphorane CS2 adduct S2CC(PPh3)2 (1) reacts with Ag(I) salts which contain weakly coordinating anions such as [BF4]- or [Al{OC(CF3)3}4]- to produce the cluster compounds [Ag6{S2CC(PPh3)2}4][BF4]6 (2) and [Ag4{S2CC(PPh3)2}4][Al{OC(CF3)3}4]4 (3), respectively, as orange yellow crystals containing solvent molecules. In the solid state the Ag4 unit in 3 forms a tetrahedron, and in the Ag6 core of 2 two of the opposite edges of the tetrahedron are bridged by Ag+ ions. The clusters are held together by argentophilic interactions, and each sulfur atom of 1 is coordinated to four (as in 2) or three (as in 3) silver atoms. The compounds are characterized by IR and 31P NMR spectroscopic studies and by X-ray diffraction analyses.