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This work reports the one-pot synthesis of sterically demanding aniline derivatives from aryllithium species utilising trimethylsilyl azide to introduce amine functionalities and conversions to new examples of a common <i>N,N</i>′-chelating ligand system. The reaction of TripLi (Trip = 2,4,6-<i>i</i>Pr₃-C₆H₂) with trimethylsilyl azide afforded the silyltriazene TripN₂N(SiMe₃)₂ in situ, which readily reacts with methanol under dinitrogen elimination to the aniline TripNH₂ in good yield. The reaction pathways and by-products of the system have been studied. The extension of this reaction to a much more sterically demanding terphenyl system suggested that TerLi (Ter = 2,6-Trip₂-C₆H₃) slowly reacted with trimethylsilyl azide to form a silyl(terphenyl)triazenide lithium complex in situ, predominantly underwent nitrogen loss to TerN(SiMe₃)Li in parallel, which afforded TerN(SiMe₃)H after workup, and can be deprotected under acidic conditions to form the aniline TerNH₂. TripNH₂ was furthermore converted to the sterically demanding <i>β</i>-diketimines ^RTripnacnacH (=HC{RCN(Trip)}₂H), with R = Me, Et and <i>i</i>Pr, in one-pot procedures from the corresponding 1,3-diketones. The bulkiest proligand was employed to synthesise the magnesium hydride complex [{(^iPrTripnacnac)MgH}₂], which shows a distorted dimeric structure caused by the substituents of the sterically demanding ligand moieties.