S-Cylindrophanes: From Metal Tweezers to Metal Sandwiches

Inclusion of AgI and CuI ions by the preorganized cylindrophane cage compound 1 provides the first examples of bis(η6) sandwich complexes of these metals. Locked in a trigonal-planar heteroatom ligand field, the guest ions are shown by NMR spectroscopy to withdraw electron density from the aromatic rings. A statistical study of η6 coordination in the solid state supports the description of arene–metal contacts between 2.5 and 3.5 Å as bonds.