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

Abstract The reduction of (Ph 3 P)AuCl with NaBH 4 in the presence of HSC(SiMe 3 ) 3 , leads to one of the largest metalloid gold clusters: Au 108 S 24 (PPh 3 ) 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 Au 48 S 24 shell, a novel building block in gold chemistry. The protecting Au 48 S 24 shell is completed by additional 16 Au(PPh 3 ) 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: M n R m ( n > m ).