Reaction of 1,8-C10H6{NHSiMe3}(2) (1) With 2 molar equiv of butyllithium in toluene and subsequently added hmpa or tmeda as neutral coligands yields the lithium compounds [1,8-C10H6{N(Li-hmpa)SiMe3}(2)] (2) or [1,8-C10H6{N(Li)SiM3}(2)(tmeda)(1.5)](2) (3), respectively which were both characterized by X-ray crystallography. Both compounds were obtained irrespective of the amide/coligand ratio in solution. Compound 3 is a dimeric complex containing two chelating and one bridging tmeda ligand. Lithiation of 1 in thf and reaction of the lithium amide with MgBr2(Et2O) gave the mixed-metal Li-Mg-amide [1,8-C10H6{NSiMe3}(2)Li(thf)MgBr(thf)] (4). A single-crystal X-ray structure analysis revealed that in the solid the MgBr units coordinate to neighboring lithium centers, leading to the aggregation of the molecules as polymeric chains.