Isocyanide Cu(I) complexes with unexpected μ₂‐bridging pseudohalides: Synthesis, characterization and catalytic activity towards CuAAC

Three neutral Cu(I) complexes bearing 2,6-dimethylphenyl isocyanide (CNXyl) and different triatomic pseudohalogens (SCN−, OCN− N3−) as ligands were efficiently synthesized characterized. The solid-state structures unambiguously determined through single-crystal X-ray diffraction, revealing unexpected bridging coordination modes in the case of N3−. All tested for azide-alkyne cycloaddition (CuAAC), showing interesting catalytic activity towards formation 1,4-disubstituted-1,2,3-triazoles cyanato azido complexes. Both species afforded yields above 90% with 0.5 mol% catalyst at 50°C 24 h. Several alkynes azides using more active complex, affording corresponding triazoles high yields. complex also induced intramolecular CuAAC presence dimethyl acetylenedicarboxylate benzyl bromide/phenylacetylene.