β-Diketiminate (BDI) ligands are widely used supporting ligands in modern organometallic chemistry and are capable of stabilizing various metal complexes in multiple oxidation states and coordination environments. This review describes recent advances in the chemistry of group 5 metals, namely vanadium, niobium and tantalum supported by the BDI ligand framework. Special emphasis is put on the reactivity of low-valent complexes, as well as low-coordinate complexes containing reactive multiply bonded groups, such as alkylidene, imido and nitrido groups.