Synthesis of the First Isolable Geminal 1,1‐Dilithiostannane and Its Intriguing Structural Diversity

Abstract The synthesis of the first isolable geminal 1,1‐dilithiostannane is reported. In the solid state, the novel 1,1‐dilithiostannane has three different structural motifs, depending on the reaction conditions used for its synthesis: (1) an unsolvated co‐aggregate consisting of two 1,1‐dilithiostannane molecules and two silyllithium molecules, {[( t Bu 2 MeSi) 2 SnLi 2 ] 2 ⋅ [ t Bu 2 MeSiLi] 2 }; (2) a solvated trimeric stannyllithium dianion {[( t Bu 2 MeSi) 2 Sn] 3 Li 4 } 2− associated with two fully dissociated THF‐solvated Li + cations; (3) a THF‐solvated contact‐ion pair dimer of 1,1‐dilithiostannane, [( t Bu 2 MeSi) 2 SnLi 2 ] 2 ⋅ (THF) 4 .