Organometallic Reactivity of [Silver(I)­(Pyridine‐Containing Ligand)] Complexes Relevant to Catalysis

Silver(I) complexes of pyiridine-containing macrocyclic ligands (Pc-L) have already been demonstrated as active catalysts for some domino and multicomponent reactions. Here, we report new chiral [Ag-I(Pc-L*)] cationic complexes that have been synthesized and fully characterized, including structural determination by single-crystal X-ray diffraction. The complexes show a rich coordination chemistry, demonstrating both the sigma-philic (alcohol and nitrile coordination) and the -philic (alkyne coordination) nature of silver. The (2) coordination mode of the naphthyl pendant arm of the ligands on silver has been observed in solution by NMR spectroscopic experiments. 2D NMR spectroscopy revealed the presence of positive cross peaks resulting from rotational processes and the rate of rotation was measured by using 2D exchange spectroscopy (EXSY).