Silver Clusters Stabilized by Fe(Co)4 Ligands

Abstract

ABSTRACTThe reaction of [Fe(CO)4]2− with Ag+ in tetrahydrofuran or acetonitrile solution affords a series of silver clusters stabilized by Fe(CO)4 pseudo-ligands, formally arising from oligomerization of [AgFe(CO)4]− and their subsequent condensation with Ag+/O/−. The [Ag4Fe4(CO)16]4−, [Ag5Fe4(CO)16]3−, and [Ag13Fe8(CO)32]4− anions have been structurally characterized by X ray studies, while the formulation of all the remaining species is presently based on analytical and spectroscopic characterization, as well as their chemical behavior. Attempts to isolate the [Ag6Fe4(CO)16]2− salts in a crystalline state were unsuccessful due to their ready oligomerization to completely insoluble material of [(Ag+)n{[Ag6Fe4(CO)16]2−}n+1](n+2)− composition. This material is depolymerized by dimethylsulfoxide or by addition of stoichiometric amounts of amines and, upon dissolution, gives the [Ag6Fe4(CO)16]2− dianion.