A first structurally characterized primary aminophosphane (Ar2PNH2 (2); Ar = 2,4,6-iPr(3)C(6)H(2)) that is a stable solid at room temperature without decomposition by self-condensation is reported. Reactions of N-phosphanyllithium amide (tBu(2)PNHLi (3)) with Me2SiCl2 and MeSiCl3 in Et2O result in the formation of Me2Si(NHPtBu2)(2) (4) and MeSi(NHPtBu2)(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 AIMe(3) yielded the trialuminum complex MeSi[N(AIMe(2))PtBu2](3) (8). These three complexes were investigated by microanalysis and multinuclear NMR spectroscopy. The dilithium complex [Me2Si(NLiPtBu2)(2)center dot 3THF] (6) and the trilithium complex [MeSi(NLiPtBu2)(3)center dot 3Et(2)O] (7) were further characterized by single-crystal X-ray structural analysis.