The experimental trend observed for the reactivity of cl-block nitrido complexes is one of increasing electrophilicity of the nitrogen ligand, upon going from early (group 4) to later (group 8) transition metals. Accordingly nitrido complexes of group 8 frequently react with electron donors despite the formal N(3-) formulation of the nitrido ligand would suggest nucleophilic behaviour. A number of typically applied population analyses from the literature have been used in a DFT framework to investigate their ability to reproduce this observed trend. It is found that population analyses in comparative studies are valuable tools and that the partial charges on the nitrogen atom vary in accordance with experimental reactivity for a set of model complexes with a fixed ligand sphere and oxidation state. Both negatively charged, [M(N)Cl(4)](2-), and neutral complexes, [M(N)salen], (in both cases M = V(V), Cr(V), Mn(V) and Fe(V)) follow this trend.