Synthesis and Crystal Structure of {[HNEt3]2n[Ag 8Ag4/2(SC6H4tBu-4) 12]n· nC2H5OH} and Its Reaction Product with CS2

By using an arylthiolate ligand with a substituent in the paraposition, 4-tBuC6H4S-, the yellow silver-thiolate complex {[HNEt3]2n[Ag8Ag4/2(SC 6H4tBu-4)12]n·nC 2H5OH} (1) has been synthesized and structurally characterized. Complex 1 is ionic composed of [HNEt3]+ cations and a polymeric [Ag8Ag4/2(SC6H 4tBu-4)12]n 2n- anion. Complex 1 reacts with CS2 in acetone to give a red pentaconta-nuclear silver anionic cluster complex {[HNEt3]4[Ag50S 7(SC6H4tBu-4)40]·2CS 2· 6C3H6O} (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.