Self-assembled coordination thioether silver(I) macrocyclic complexes for homogeneous catalysis

Article abstract of DOI:10.3762/bjoc.15.239

The bis-ortho-thioether 9,10-bis[(o-methylthio)phenyl]anthracene was synthesized as a syn-atropisomer, as revealed by X-ray diffraction. This alkylaryl thioether ligand (L) formed different macrocyclic complexes by coordination with silver(I) salts depending on the nature of the anion: M₂L₂ for AgOTf and AgOTFA, M₆L₄ for AgNO₃. A discrete M₂L complex was obtained in the presence of bulky PPh₃AgOTf. These silver(I) complexes adopted similar structures in solution and in the solid state. As each sulfur atom in the ligand is prochiral, macrocycles L₂M₂ were obtained as mixtures of diastereoisomers, depending on the configurations of the sulfur atoms coordinated to silver cations. The X-ray structures of the two L₂·(AgOTf)₂ stereoisomers highlighted their different geometry. The catalytic activity of all silver(I) complexes was effective under homogeneous conditions in two tandem addition/cycloisomerization of alkynes using 0.5-1 mol % of catalytic loading.