| Abstract: | 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. |
