LAUSR

Abstract The diorganoselenide [Me2C(OH)CH2]2Se (1) was prepared by reacting the in situ obtained Na2Se with 1‐chloro-2‐methyl‐2‐propanol. Reactions of 1 and [2-(Me2NCH2)C6H4]2Se (2) with appropriate silver(I) salts in 1:1 molar ratio resulted in metal complexes of type [Ag(X)Se{CH2C(OH)Me2}2] [X = OSO2CF3 (OTf) (3), OClO3 (4)] and [Ag(X)Se{C6H4(CH2NMe2)-2}2] [X = OSO2CF3 (5), ONO2 (6)], respectively. The ligand 1 and the silver complexes were investigated by appropriate spectroscopic methods, both in solution and in solid state: multinuclear NMR (1H, 13C, 19F, 77Se), ESI+ mass spectrometry, IR spectroscopy and molar conductivity. The metal complexes behave as 1:1 electrolytes in 10−3 MeOH solutions, while in solid state the anionic ligands behave as monodentate moieties. Complexes 4 and 5 were investigated by single‐crystal X‐ray diffraction. The crystal of 4 contains two similar independent molecules, 4a and 4b, for which was observed the migration of one OH hydrogen from ligand 1 to the OClO3 group, thus resulting in [Ag(HClO4)Se{OCCH2Me2}{(OH)CCH2Me2}], where ligand 1 behaves as a O,Se monometallic biconective moiety. In 5 the ligand 2 acts as a N,Se,N monometallic triconective moiety. In both compounds Ag(I) is surrounded by the donor atoms in a trigonal pyramidal coordination geometry. Strong Se→Ag intermolecular interactions in 4 resulted in 1D coordination polymers built by 4a and 4b molecules, respectively, while in the crystal of 5 no interaction between heavy atoms was observed. Supramolecular networks based on H‧‧‧O contacts are formed in both compounds.