Dihalogen-templated synthesis of dodecanuclear silver dichalcogenophosphate clusters

Dodecanuclear silver clusters, Ag-12(mu(5)-X)(2)[E2P(OEt)(2)](10) (X = Br, I; E = S, Se), were isolated from the reaction of [Ag(CH3CN)(4)](PF6), dichalcogenophosphate ammonium salts and halides in a common organic solvent. The Ag-12 ring consists of two identical Ag-6 units linked by intermolecular Ag-E bonds. The geometry of a Ag-6 motif can be described as a bicapped tetrahedron, which is stabilized by a rare pentacoordinated bromine/iodine atom as well as five 1,1-dichalcogenophosphate ligands.