Reaction of aryl azides with tris(trimethylsilyl)silyllithium: Synthesis of tmeda or thf adducts of [Li{N(Ar)Si(SiMe3)3}] and 1,4-trimethylsilyl migration from oxygen to nitrogen

Reaction of ArN3 (Ar = Ph, p-MeC6H4, 1-naphthyl) with [Li{Si(SiMe3)3}(thf)3] yielded lithium amides [Li{N(Ar)Si(SiMe3)3}L] (L = tmeda or (thf)2). Similar treatment of o-phenylene diazide with 2 equiv. of [Li{Si(SiMe3)3}(thf)3] formed dilithium diamide complex 4. Reaction between o-Me3SiOC6H4N3 and [Li{Si(SiMe3)3}(thf)3] afforded, via 1,4-trimethylsilyl migration from oxygen to nitrogen, [Li{OC6H4{N(SiMe3)Si(SiMe3)3}-2}]2 (5). The structures of complexes 3 and 5 have been determined by single crystal X-ray diffraction techniques.