Novel μ 5 ‐Coordination Modes of Aryl and Alkyl Ethynides and Classification of Metal–Ligand Interactions in Silver( I ) Complexes

Novel μ 5 ‐η 1 ,η 1 ,η 1 ,η 1 ,η 2 and μ 5 ‐η 1 ,η 1 ,η 1 ,η 2 ,η 2 coordination modes of alkyl and aryl ethynide moieties are found in silver( I ) complexes 1 – 5 , and the metal–ligand distances can be classified into σ, π and mixed (σ,π) types. With the consistent square‐pyramidal capping Ag 5 baskets of the ethynide moiety as supramolecular synthons, a series of two‐ and three‐dimensional coordination networks are obtained.