New examples of the exploitation of intermediary ligands in the synthesis of polymeric (μ-Se)Hg-clusters

(PhSe)2Hg reacts initially with HgX2 (X = Cl, I) and further with triphenylphosphine/DMF to give [(PhSe)7Hg4ClPy]n (1) and [(PhSe)7Hg4I(DMF)]n (2), polymeric assemblies of (μ-Se)Hg clusters obtained through coordinating intermediary ligands. Each single adamantoid molecule of 1 and 2 presents the HgII ions with a distorted tetrahedral configuration linked through asymmetric [μ-(Ph)Se]− bridges. [(PhSe)7Hg4ClPy]n and [(PhSe)7Hg4I(DMF)]n are further examples of extended one-dimensional chains of closed anisotropic ME (E = S, Se, Te) systems. In these reactions the features of the intermediary ligands should determine the template which leads to single adamantane moieties or to fused ones.