Dihalogen-templated synthesis of dodecanuclear silver dichalcogenophosphate clusters

Abstract

Dodecanuclear silver clusters, Ag₁₂(μ₅-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 Ag₁₂ ring consists of two identical Ag₆ units linked by intermolecular Ag–E bonds. The geometry of a Ag₆ 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.