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.
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