We report the syntheses of 2-pyridylimido complexes of tantalum and niobium by N=N bond cleavage of 2,2'-azopyridine. Reaction of MCl5 (M = Ta and Nb) with 2,2'-azopyridine in the presence of 0.5 equiv of 1-methyl-3,6-bis(trimethylsilyl)-1,4-cyclohexadiene (abbreviated Si-Me-CHD) afforded a dark red solution (for Ta) and a dark blue solution (for Nb) with some insoluble precipitates. After removing the solids, another 0.5 equiv of Si-Me-CHD was added to each solution, giving [M(=Npy)Cl-3](n) (1a: M = Ta; 1b: M = Nb) through reductive cleavage of the N=N bond of 2,2'-azopyridine. The initial products of the above reactions were determined to be 2,2'-azopyridine-bridged dinuclear complexes, [(MCl4)(2)(mu-pyNNpy)] (2a: M = Ta; 2b: M = Nb), which were isolated by treating MCl5 with 2,2'-azopyridine and Si-Me-CHD in a 2:1:1 molar ratio. In 2a and 2b, the N=N bond was reduced to a single bond via two-electron reduction. Further reduction of complexes 2a and 2b with 1 equiv of Si-Me-CHD afforded complexes la and 1b. An anionic doubly mu-imido-bridged ditantalum complex, [(Bu4N)-Bu-n][Ta-2(mu-Npy)(2)Cl-7] (3a), was generated upon addition of (Bu4NCl)-Bu-n to complex 1a, while addition of (Bu4NCl)-Bu-n to niobium complex 1b gave a polymeric terminal imido complex, [(B4N)-B-n](n/2)[{Nb(=Npy)Cl-3}(2)(mu-Cl)](n/2) (3b). Complexations of la and 1b with 1 equiv of 2,2'-bipyridine resulted in the formation of mononuclear 2-pyridylimido complexes, M(=Npy)Cl-3 (bipy) (4a: M = Ta; 4b: M = Nb), whose main structural feature is intramolecular hydrogen bonding between the ortho hydrogen atom of 2,2'-bipyridine and the nitrogen atom of the pyridyl group on the imido ligand. Isolated 2-pyridylimido complexes 4a and 4b reacted with [RhCl(cod)] 2 to produce the corresponding early-late heterobimetallic complexes, (bipy)MCl3(mu-Npy)RhCl(cod) (5a: M = Ta; 5b: M = Nb).