Solid‐State Reactions of AgAc with TabHPF₆ at Room Temperature − Isolation and Structural Characterisation of an Unusual Octadecanuclear Silver Thiolate Cluster [Ag₉(Tab)₈(MeCN)₈]₂(PF₆)₁₈·4MeCN [Tab = 4‐(trimethylammonio)benzenethiolate]

Abstract

Abstract The room‐temperature solid‐state reaction of silver acetate with TabHPF 6 [Tab = 4‐(trimethylammonio)benzenethiolate] followed by recrystallization from MeCN afforded a unique octadecanuclear silver thiolate complex [Ag 9 (Tab) 8 (MeCN) 8 ] 2 (PF 6 ) 18 ·4MeCN ( 1 ). An X‐ray analysis of 1 revealed that the structure of [Ag 9 (Tab) 8 (MeCN) 8 ] 2 18+ contains an unprecedented tubular motif in which one central saddle‐shaped Ag 6 S 6 fragment and two identical Ag 5 S 6 fragments are interconnected by a pair of Ag atoms and four Ag−S bonds. The solid‐state product was assumed to be [Ag 9 (Tab) 8 ] 2 (PF 6 ) 18 and might have the Ag 18 S 16 core structure of 1 based on elemental analysis, IR spectroscopy, 1 H NMR spectroscopy, luminescence spectra, XRD and TGA measurements. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)