Incomplete nitrogen atom transfer from the iron(IV) nitride complex PhB(MesIm)(3)Fe equivalent to N to the vanadium-(III) complex V(Mes)(3)(THF) quantitatively provides the bimetallic complex PhB(MesIm)(3)Fe-N=V(Mes)(3). Structural and spectroscopic characterizations reveal that the nitride ligand forms a linear bridge between V(V) and high-spin Fe(II) metal ions, confirming that atom transfer is accompanied by electron transfer. In the presence of an applied dc field, the complex displays slow relaxation of the magnetization, revealing its single-molecule magnet properties with an estimation of the energy barrier at about 10 K. This complex establishes a synthetic principle for the assembly of paramagnetic complexes bridged by nitride ligands.