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Zero-valent iron, cobalt, and nickel were installed into the metalloligand V[N(o-(NCH2P(iPr)2)C6H4)3] (1, VL), generating the heterobimetallic trio FeVL (2), CoVL (3), and NiVL (4), respectively. In addition, the one-electron-oxidized analogues [FeVL]X ([2ox]X, where X- = BPh4 or PF6) and [CoVL]BPh4 ([3ox]BPh4) were prepared. The complexes were characterized by a host of physical methods, including cyclic voltammetry, X-ray crystallography, magnetic susceptibility, electronic absorption, NMR, electron paramagnetic resonance (EPR), and Mössbauer spectroscopies. The CoV and FeV heterobimetallic compounds have short M-V bond lengths that are consistent with M-M multiple bonding. As revealed by theoretical calculations, the M-V bond is triple in 2, 2ox, and 3ox, double in 3, and dative (Ni → V) in 4. The (d-d)10 species, 2 and 3ox, are diamagnetic and exhibit large diamagnetic anisotropies of '4700 × 10-36 m3/molecule. Complexes 2 and 3ox are also characterized by intense visible bands at 760 and 610 nm (ε > 1000 M-1 cm-1), respectively, which correspond to an intermetal (M → V) charge-transfer transition. Magnetic susceptibility measurements and EPR characterization establish S = 1/2 ground states for (d-d)9 2ox and (d-d)11 3, while (d-d)12 4 is S = 1 based on Evans' method.