The chalcogen bond (ChB) is a noncovalent attraction between an electrophilic chalcogen atom and a nucleophilic (Nu) region in the same (intramolecular) or another (intermolecular) molecular entity: R-Ch⋯Nu (Ch = O, S, Se or Te; R = substituents; Nu = nucleophile). ChB is comparable to the hydrogen and halogen bonds both in terms of strengths and directionality. However, in contrast to the monovalent halogen atoms, usually the divalent or tetravalent chalcogen atoms are able to display more than one electrophilic centre (on account of the existence of two or three species bonded to the chalcogen atom), which provides an additional opportunity in the use of this type of noncovalent binding in synthetic operations. In this work, the role of ChB at the secondary coordination sphere of metal complexes through copper(II)-mediated activation of dioxygen or of one nitrile group of a 1,2,5-selenadiazole-3,4-dicarbonitrile ligand to form a carbimidate or an imino-carboxylic acid is demonstrated. DFT calculations allowed evaluation of the strength of the ChBs and proved their relevant structure directing role in the solid state architectures. The effect of metal-coordination on the σ-hole opposite to the coordinated SeO bond has been analysed using molecular electrostatic potential (MEP) surfaces and explains the greater ability of the coordinated selenoxide derivatives to form strong ChBs.