Ethynide-stabilized high-nuclearity silver() sulfido molecular clusters assembled using organic sulfide precursors

Inexpensive 1,1′-thiocarbonyldiimidazole and di(2-pyridyl) thionocarbonate have been used as respective sulfide precursors to assemble unprecedented high-nuclearity ethynide-stabilized silver( i ) sulfido molecular clusters [Ag 9 S 6 @Ag 36 (C&z.tbd;C t Bu) 32 (H 2 O) 2 ] [Ag(imidazole)(CH 3 OH)(H 2 O)](BF 4 ) 2 ·8H 2 O·2CH 3 OH ( 1 ) and [Ag 120 S 24 (PhC&z.tbd;C) 52 Cl 4 (2-pyridone) 10 (H 2 O) 8 ](H 3 O) 4 (SiF 6 ) 8 (BF 4 ) 4 ·CH 3 OH·22H 2 O ( 2 ), the latter being the largest isolated silver( i ) ethynide cluster reported to date. Two unprecedented molecular clusters bearing Ag 9 S 6 @Ag 36 and Ag 120 S 24 cores stabilized by surface ethynide ligands are assembled using novel organic sulfide precursors and structurally characterized by single-crystal X-ray analysis. The figure shows the Ag 120 S 24 (PhC&z.tbd;C) 52 core unit of the latter cluster.