Ag₁₀₈(PEt₃)₂₄Cl₆: A Hexagonal Prismatic Metalloid Cluster

Abstract

The ligands used for the protection of metalloid clusters heavily influence the resulting structure and shape. For silver, thiolate and alkynyl ligands are commonly used, while phosphines usually play a minor role as co‐ligands. Herein, we report the synthesis and structural characterization of Ag108(PEt3)24Cl6 (1), the largest structurally characterized metalloid silver cluster with phosphines and halides as sole ligands. Instead of the frequently observed spherical shape of metalloid clusters, 1’s structure resembles a hexagonal prism. The highly light and temperature sensitive compound features many similarities to its smaller congener Ag64(PnBu3)16Cl6, though there are distinct structural and electronic differences present. Within 1, a Ag64 subunit can be found, which identifies these clusters as molecular seeds for the formation of faceted nanoparticles.