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Interaction of [ReNCl3(PPh3)2] or [ReOCl2(PPh3)3] with NaLOEt (LOEt = [Co(η5-C5H5){PO(OEt)2}3]) afforded [ReLOEtN(PPh3)Cl] 1 and [ReLOEtOCl2] 2, respectively. Reaction of 1 with AgBF4 gave the nitridorhenium(VI) complex [ReLOEtN(PPh3)Cl]BF41·BF4, which has a μeff of 1.8 μB. Treatment of 1 with MeOSO2CF3, PhCH2Br or [Ph3C]BF4 afforded the respective organoimido species [ReLOEt(NMe)(PPh3)Cl][CF3SO3] 3, [ReLOEt(NCH2Ph)(PPh3)Cl]Br 4, and [ReLOEt(NCPh3)(PPh3)Cl] 5. Reaction of 1 with [Au(PPh3)(CF3SO3)], [Ru(Et2dtc)(PPh3)2(CO)(CF3SO3)], or [ReMeO3] yielded the bimetallic nitrido complexes [Au(PPh3){NReLOEt(PPh3)Cl}][CF3SO3] 6, [Ru(Et2dtc)(PPh3)(H2O)(CO){NReLOEt(PPh3)Cl}][CF3SO3] 7 or [ReMeO3{NReLOEt(PPh3)Cl}] 8, respectively. Treatment of [NBu4n][OsNCl4] with NaLOEt gave [OsLOEtNCl2] 9. The average Os–O, Os–Cl and Os–N distances in 9 are 2.066, 2.289 and 2.58(1) A, respectively. Reaction of 9 with PPh3 afforded the osmium(IV) phosphoran iminate species [OsLOEt(NPPh3)Cl2] 10, which has a μeff of 2.0 μB. The average Os–O, Os–Cl and Os–N distances in 10 are 2.099, 2.342, 1.893(5) A, respectively, the Os–N–P angle being 137.5(3)°. The formal potentials of the LOEt–Re and –Os complexes have been determined by cyclic voltammetry. On the basis of the ReVI–ReV formal potential, the π-donor strength was found to decrease in the order N3− > [NAu(PPh3)]2− > NMe2−.