Synthese und Struktur von Lithium-tris(trimethylsilyl)silanid · 1,5 DME

Synthesis and Structure of Lithium Tris(trimethylsilyl)silanide · 1,5 DME Lithium tris(trimethylsilyl)silanide · 1,5 DME 2a synthesized from tetrakis(trimethylsilyl)silane 1 6] and methyllithium in 1,2-dimethoxyethane , crystallizes in the monoclinic space group P2₁/c with following dimensions of the unit cell determined at a temperature of measurement of ?120 ± 2°C: a = 1 072.9(3); b = 1 408.3(4); c = 1 775.1(5) pm; β = 107.74(2)°; 4 formula units (Z = 2). An X-ray structure determination (R_w = 0.040) shows the compound to be built up from two lithium tris(trimethylsilyl)silanide] moieties which are connected via a bridging DME molecule. Two remaining sites of each four-coordinate lithium atom are occupied by a chelating DME ligand. The Li? Si distance of 263 pm is considerably longer than the sum of covalent radii; further characteristic mean bond lengths and angles are: Si? Si 234, Li? O 200, O? C 144, O?O (biß) 264 pm; Si? Si? Si 104°, Li? Si? Si 107° to 126°; O? Li? O (inside the chelate ring) 83°. Unfortunately, di(tert-butyl)bis(trimethylsilyl)silane 17 prepared from di(tert-butyl)dichlorsilane 15 , chlorotrimethylsilane and lithium, does not react with alkyllithium compounds to give the analogous silanide.