The triazenide complexes cis-[M(C6F5)2(η2-ArNNNAr)] − (M = Pd, Pt; Ar = C6H5, C6H4Me-p), anti-[{Pd(C6F5)(L)(μ-PhNNNPh)}2] [L = PPh3, t-BuNC, PhCN, tht (tht = SC4H8, tetrahydrothiophene)] and anti-[{Pd(C6F5)(Br)(μ-PhNNNPh)}2]2− have been prepared by treatment of the corresponding precursors [{M(C6F5)2(μ-OH)}2]2− (M = Pd, Pt), [{Pd(C6F5)(L)(μ-X)}2] (X = OH or Cl) and [{Pd(C6F5)(Br)(μ-Br)}2]2− with either ArNNNHAr or ArNNNAr−. The stereoselective oxidation of cis-[Pt(C6F5)2(PhNNNPh)]− with PhICl2 or I2 leads to the synthesis of the corresponding mononuclear platinum(IV) complex cis,trans-[Pt(C6F5)2(PhNNNPh)(X)2]− (X = Cl or I). The crystal structures of cis-[Pd(C6F5)2(η2-PhNNNPh)]−, anti-[{Pd(C6F5)(t-BuNC)(μ-PhNNNPh)}2] and cis,trans-[Pt(C6F5)2(η2-PhNNNPh)(Cl)2]− have been established by X-ray diffraction. The Pd⋯Pd distance bridged by the rigid triazenido ligands in anti-[{Pd(C6F5)(t-BuNC)(μ-PhNNNPh)}2] is 2.9907(8) A where a boat conformation of the central ‘Pd2N6’ eight-membered ring is observed. The [Pt(C6F5)2(η2-PhNNNPh)(Cl)2]− anion shows an octahedral arrangement around the platinum atom, involving two trans-chloro ligands, two cis-C6F5 groups and a chelating triazenide.