Polymerization Isomerism in Co-M (M = Cu, Ag, Au) Carbonyl Clusters: Synthesis, Structures and Computational Investigation.

The reaction of [Co(CO)] () with M(I) compounds (M = Cu, Ag, Au) was reinvestigated unraveling an unprecedented case of polymerization isomerism. Thus, as previously reported, the trinuclear clusters [M{Co(CO)}] (M = Cu, ; Ag, ; Au, ) were obtained by reacting with M(I) in a 2:1 molar ratio. Their molecular structures were corroborated by single-crystal X-ray diffraction (SC-XRD) on isomorphous [NEt][M{Co(CO)}] salts. NEtrepresented the first structural characterization of . More interestingly, changing the crystallization conditions of solutions of , the hexanuclear cluster [Ag{Co(CO)}] () was obtained in the solid state instead of . Its molecular structure was determined by SC-XRD as Na()·CHO, PPN·CH (PPN = N(PPh)]), NBu and NMe salts. may be viewed as a dimer of and, thus, it represents a rare case of polymerization isomerism (that is, two compounds having the same elemental composition but different molecular weights) in cluster chemistry. The phenomenon was further studied in solution by IR and ESI-MS measurements and theoretically investigated by computational methods. Both experimental evidence and density functional theory (DFT) calculations clearly pointed out that the dimerization process occurs in the solid state only in the case of Ag, whereas Cu and Au related species exist only as monomers.