Synthesis and crystal structure of {[HNEt3]2n[Ag8Ag4/2(SC6H4tBu-4)12]n• nC2H5OH} and its reaction product with CS2

By using an arylthiolate ligand with a substituent in the paraposition, 4-tBuC(6)H(4)S(-), the yellow silver-thiolate complex {[hNEt(3)](2)[Ag8Ag4/2(SC(6)H(4)tBu-4)(12)](n).C2H5OH} (1) has been synthesized and structurally characterized. Complex 1 is ionic composed of [HNEt3](+) cations and a polymeric [Ag8Ag4/2(SC(6)H(4)tBu-4)(12)](n)(2n-) anion. Complex 1 reacts with CS2 in acetone to give a red pentaconta-nuclear silver anionic cluster complex {[HNEt3](4)[Ag50S7(SC(6)H(4)tBu-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. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004).