Tetracopper(I) thiolate- and amido-(SNS) complexes and copper-catalyzed azide-alkyne cycloaddition in water

Two tetranuclear Cu(I) complexes bearing thiolate- and amido-SNS ligands were characterized by X-ray diffraction and mass spectrometry. Although the amido ligand undergoes irreversible N-protonation by the copper-bound alkyne, the thiolate complex demonstrates good activity in the copper-catalyzed azide-alkyne cycloaddition reaction with a variety of substrates. The base-free reactions are performed in water and afford excellent yields over 2 h at 70 °C. DFT calculations suggest a proton-shuttle role for the thiolate donor in formation of the initial dicopper σ,π-alkynyl intermediate.