A first structurally characterized primary aminophosphane (Ar 2PNH 2 ( 2); Ar = 2,4,6- iPr 3C 6H 2) that is a stable solid at room temperature without decomposition by self-condensation is reported. Reactions of N-phosphanyllithium amide ( tBu 2PNHLi ( 3)) with Me 2SiCl 2 and MeSiCl 3 in Et 2O result in the formation of Me 2Si(NHP tBu 2) 2 ( 4) and MeSi(NHP tBu 2) 3 ( 5), respectively. Subsequent treatment of 4 and 5 with 2 and 3 equiv of nBuLi gave the dilithium ( 6) and trilithium ( 7) complexes, respectively. Further treatment of 5 with 3 equiv of AlMe 3 yielded the trialuminum complex MeSi[N(AlMe 2)P tBu 2] 3 ( 8). These three complexes were investigated by microanalysis and multinuclear NMR spectroscopy. The dilithium complex [Me 2Si(NLiP tBu 2) 2.3THF] ( 6) and the trilithium complex [MeSi(NLiP tBu 2) 3.3Et 2O] ( 7) were further characterized by single-crystal X-ray structural analysis.