Synthesis and Crystal Structure of {[HNEt 3 ] 2 n [Ag 8 Ag 4/2 (SC 6 H 4 t Bu‐4) 12 ] n · n C 2 H 5 OH} and Its Reaction Product with CS 2

By using an arylthiolate ligand with a substituent in the para ‐position, 4‐ t BuC 6 H 4 S − , the yellow silver‐thiolate complex {[HNEt 3 ] 2 n [Ag 8 Ag 4/2 (SC 6 H 4 t Bu‐4) 12 ] n · n C 2 H 5 OH} ( 1 ) has been synthesized and structurally characterized. Complex 1 is ionic composed of [HNEt 3 ] + cations and a polymeric [Ag 8 Ag 4/2 (SC 6 H 4 t Bu‐4) 12 ] n 2 n − anion. Complex 1 reacts with CS 2 in acetone to give a red pentaconta‐nuclear silver anionic cluster complex {[HNEt 3 ] 4 [Ag 50 S 7 (SC 6 H 4 t Bu‐4) 40 ]·2CS 2 · 6C 3 H 6 O} ( 2 ). The core of the anionic cluster of 2 consists of fifty silver atoms and forty seven sulfur atoms, shaped like a discus with a diameter of ca. 2.0 nm. The factors influencing the structure and the formation mechanism of the large cluster are discussed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)