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 {(N t Bu) 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(N t Bu) 3 2 - dianion and subsequent formation of cubane-type structures of the metal tert -butylamides. In the reaction of GeCl 2 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)(N t Bu) 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 CaLi 2 {(N t Bu) 3 S} 2 ], 3, [(thf) 2 Ba 2 Li{N(SiMe 3 ) 2 }{(N t Bu) 3 S} 2 ], 4, and [(thf)LiSn{N(SiMe 3 ) 2 }{(N t Bu) 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(N t Bu) 3 2 - dianion like the flexible electronic structure, the favorable cap-shaped geometry, and the Lewis base character of the central sulfur atom.