Syntheses and structures of main group metal complexes of the S(NtBu)32- dianion, an inorganic Y-conjugated tripod

The metal metathesis reactions of [Li-4{((NBu)-Bu-t)(3)S}2], 1, With various main group metal compounds are investigated. The reactions of 1 with group 14 metal(II) halides result in decomposition of the S((NBu)-Bu-t)(3)(2-) dianion and subsequent formation of cubane-type structures of the metal tert-butylamides. In the reaction of GeCl2 with 1 a Ge=S double bond is formed. While the use of 1.thf initiates a complex redox reaction affording the mixed-valence Ge(II)/Ge(IV) complex [Ge-4(S)((NBu)-Bu-t)4], 2, partial metal metathesis is achieved by employing metal(II) bis[bis(trimethylsilyl)amides] in reactions with 1. The mixed-metal complexes [(thf)(2)CaLi2{((NBu)-Bu-t)(3)s}2], 3, [(thf)(2)Ba2Li{N(SiMe3)(2)}{(NBu)-Bu-t)(3)S}(2)] 4, and [(thf)LiSn{N(SiMe3)(2)}-{((NBu)-Bu-t)(3)S}], 5, were synthesized and structurally investigated. A closer inspection of the structural parameters of the complexes 3-5 reveals some of the intriguing ligand properties of the S((NBu)-Bu-t)(3)(2-) dianion like the flexible electronic structure, the favorable cap-shaped geometry, and the Lewis base character of the central sulfur atom.