Synthesis and Structural Characterization of Metalated 1,8-Bis(silylamino)naphthalene Derivatives

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)SiMe3}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}2Li(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.