Air-stable rhenium(V) nitrido complexes are formed when [ReOCl3(PPh3)(2)], [NBu4][ReOCl4], or [NBu4][ReNCl4] are treated with an excess of silylated phosphoraneiminates of the composition Me3SiNPPh3 or Ph2P(NSiMe3)CH2PPh2 in CH2Cl2. Complexes of the compositions [ReNCl(Ph2PCH2PPh2NH)(2)]Cl (1), [ReN(OSiMe3)(Ph2PCH2PPh2NH)(2)]Cl (2) or [ReNCl2(PPh3)(2)] (3) were isolated and structurally characterized. The latter compound was also produced during a reaction of the rhenium(III) precursor [ReCl3(PPh3)(2)(CH3CN)] and Me3SiNPPh3. Nitrogen transfer from the phosphorus to the rhenium atoms and the formation of nitrido ligands were observed in all examples. All products of reactions with an excess of the potentially chelating phosphoraneiminate Me3SiNP(Ph-2)CH2PPh2 contain neutral Ph2PCH2PPh2NH ligands. The required protons are supplied by a metal-induced decomposition of the solvent dichloromethane. The Re-N(imine) bond lengths (2.055-2.110 angstrom) indicate single bonds, whereas the N-P bond with lengths between 1.596 angstrom and 1.611 angstrom reflect considerable double bond character. An oxorhenium(V) phosphoraneiminato complex, the dimeric compound [ReOCl2(mu-N-Ph2PCH2PPh2N)](2) (4), is formed during the reaction of [NBu4][ReOCl4] with an equivalent amount of Ph2P(NSiMe3)CH2PPh2 in dry acetonitrile. The blue neutral complex with two bridging phosphoraneiminatc, units is stable as a solid and in dry solvents. It decomposes in solution, when traces of water are present. The rhenium-nitrogen distances of 2.028(3) and 2.082(3) angstrom are in the typical range of bridging phosphoraneiminates and an almost symmetric bonding mode. Technetium complexes with phosphoraneimine ligands were isolated from reactions of [NBu4][TcOCl4] with Me3SiNPPh3, and [NBu4][TcNCl4] with Me3SiNP(Ph-2)CH2PPh2. Nitrogen transfer and the formation of a five-coordinate nitrido species, [TcNCl2(HNPPh3)(2)] (5), was observed in the case of the oxo precursor, whereas reduction of the technetium(VI) starting material and the formation of the neutral technetium(V) complex [TcNCl2(Ph2PCH2PPh2NH)] (6) or [TcNCl(Ph2PCH2PPh2NH)(2)]Cl (7) was observed in the latter case. Both technetium complexes are air stable and X-ray structure determinations show bonding modes of the phosphoraneimines similar to those in the rhenium complexes.