<p>In the present study, the oxidative dissolution of metallic copper has been explored with the intention to prepare some new complexes with urotropine (<i>hmta</i>) and triethylenediamine (<i>dabco</i>) ligands. All the compounds synthesized were characterized by single-crystal X-ray diffraction and Raman spectroscopy<i>.</i> Reactions performed in a DMSO/CuCl<sub>2</sub>∙2H<sub>2</sub>O mixture resulted in [(μ-Cl)<sub>2</sub>Cu<sup>I</sup>(<i>hdabco</i><sup>+</sup>)Cu<sup>I</sup>(μ-Cl)(κ<i>S</i>-DMSO)]<sub>n</sub> and [Cu<sup>I</sup>Cl(<i>hmta</i>)<sub>2</sub>] complexes. Their isostructural bromide analogs [(μ-Br)<sub>2</sub>Cu<sup>I</sup>(<i>hdabco</i><sup>+</sup>)Cu<sup>I</sup>(μ-Br)(κ<i>S</i>-DMSO)]<sub>n</sub> and [Cu<sup>I</sup>Br(<i>hmta</i>)<sub>2</sub>] were prepared by the reaction of elemental copper with respective ligands in a DMSO/CBr<sub>4</sub> mixture. Early interrupted reaction of the copper wire with the DMSO/CBr<sub>4</sub>/<i>dabco</i> solution resulted in an appearance of crystals of the [Cu<sup>I</sup><sub>2</sub>Br<sub>2</sub>(CO)<sub>2</sub>(<i>dabco</i>)]<sub>n</sub> carbonyl complex on the copper surface. It arises with the participation of <i>in situ</i> formed carbon monoxide. Despite the identical stoichiometry, the crystal structure of the [Cu<sub>2</sub>Br<sub>2</sub>(CO)<sub>2</sub>(<i>dabco</i>)]<sub>n</sub> complex is markedly different from that of a known [Cu<sub>2</sub>Cl<sub>2</sub>(CO)<sub>2</sub>(<i>dabco</i>)]<sub>n</sub> analog.</p
