Au108S24(PPh3)16: A Highly Symmetric Nanoscale Gold Cluster Confirms the General Concept of Metalloid Clusters

The reduction of (Ph3P) AuCl with NaBH4 in the presence of HSC(SiMe3)(3), leads to one of the largest metalloid gold clusters: Au108S24(PPh3)(16) (1). Within 1 an octahedral Au-44 core of gold atoms arranged as in Au metal is surrounded by 48 oxidized Au atoms of an Au48S24 shell, a novel building block in gold chemistry. The protecting Au48S24 shell is completed by additional 16 Au(PPh3) units, leading to a complete protection of the gold core. Within 1 the Au-Au distances get more molecular on going from the center to the ligand shell. Cluster 1 represents novel structural motives in the field of metalloid gold clusters which also are partly typical for metal atoms in metalloid clusters: MnRm (n > m).