Aminophosphane complexes 3a–e have been prepared by two different pathways: (1) the thermal reaction of 2H‐azaphosphirene complex 1 with primary or secondary amine derivatives at 75 °C (3a,b,d,e) or (2) the reaction of chlorophosphane complex 2 with sodium diphenylamide (3c). In the latter case, complex 3c was obtained together with the diphosphene complex 6, thus providing evidence for the transient formation of Na/X phosphinidenoid complexes 4a,b and/or the terminal phosphinidene complex 5. Preliminary deprotonation studies, carried out on complex 3a by using lithium diisopropylamide in TMEDA in the presence of 12‐crown‐4 at low temperature, yielded a mixture of the Li/NMe2 phosphinidenoid complex 7 together with the nonligated phosphane derivative 8, which could not be separated. Complexes 3a,b,d,e and 6 were characterized by NMR and IR spectroscopy, MS, and elemental analysis. The structures of complexes 3c–e and 6 were confirmed by single‐crystal X‐ray diffraction analysis.