Preparation and crystal structure of a novel lithium thiolate cluster: [Li14(SCH2Ph)12S(TMEDA)6](TMEDA = tetramethylethylenediamine)

Abstract

The title compound, simply prepared from benzyl mercaptan, n-butyl-lithium, and TMEDA in toluene (TMEDA = tetramethylethylenediamine), crystallises as an unusual type of cluster, in which a central S atom is surrounded by a distorted cube of Li atoms, each edge of which is bridged by a benzyl thiolate group such that the twelve S atoms form a cubo-octahedron; a further six Li atoms form a large outer octahedron, each one sitting above an S–S edge, with tetrahedral co-ordination completed by a TMEDA molecule.