Silver-Ethynide Clusters with Oxovanadate Components

Variation of the reaction conditions with AgCa parts per thousand CR (R = Ph, (t) Bu), (t) BuPO3H2, (Et4N)VO3 and AgNO3 as starting materials afforded three isostructural globular neutral silver(I)-ethynide clusters incorporating the [( (t) BuPO3)(4)V4O8](4-) unit as an integral shell component, namely {(NO3)(2)@Ag-16(Ca parts per thousand CPh)(4)[( (t) BuPO3)(4)V4O8](2)(DEF)(6)(NO3)(2)}, {(NO3)(2)@Ag-16(Ca parts per thousand C (t) Bu)(4)[( (t) BuPO3)(4)V4O8](2)(DMF)(6)(NO3)(2)}center dot DMF center dot 2H(2)O and {(NO3)(2)@Ag-16(Ca parts per thousand C (t) Bu)(4)[( (t) BuPO3)(4)V4O8](2)(DMF)(6)(NO3)(2)}center dot{(NO3)(2)@Ag-16(Ca parts per thousand C (t) Bu)(4)[( (t) BuPO3)(4)V4O8](2)(DMF)(4)(py)(2)(NO3)(2)}center dot DMF center dot 5H(2)O, in which the central cavity of each Ag-16 cluster is occupied by two nitrate ions that function as a template. Furthermore, from the reaction of AgCa parts per thousand C (t) Bu with (NH4)(4)[V2O4(d,l-citrate)(2)]center dot 4H(2)O, we isolated a new high-nuclearity silver(I)-ethynide cluster [(VO4)(2)@Ag-34(Ca parts per thousand C (t) Bu)(22)(NO3)(6)]center dot 8H(2)O that encapsulates a pair of templating orthovanadate ions.