Reactions of bipyridyl-functionalized imidazole-thiones and selones with MeX (X=I, OTf) afforded sulfenyl and selenenyl cations [(NNC)EMe]X (2/3, E=S, Se). Further reactions of these main-group cations with [Cu(CHCN)]BF, Cu(OTf) furnished dicationic [{Cu(μ-I)(NNC)EMe}][Y] (5/6, Y=BF, OTf) and tricationic copper(I) complexes [Cu{(NNC)EMe}](OTf)BF (7 a/7 b) when employed [(NNC)EMe]I and [(NNC)EMe]OTf respectively. All these cationic complexes were characterized by various spectroscopic techniques, including X-ray diffraction analysis.
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