The methods of synthesis of 1,3,5-triazapentadienes (also known as imidoylamidines), as well as the preparation of their complexes, are reviewed. The former methods include mainly the Pinner, Ley and Muller syntheses, the amination of N-imidoylimidoates or of nitriles bearing strong electron-withdrawing groups, the desulfurizing amination of N-tiobenzoylbenzamidines and the reaction of perfluoro-5-aza-4-nonene with primary amines. The synthetic procedures for the complexes involve not only the coordination of a pre-formed 1,3,5-triazapentadiene but also the generation in situ of such a species, namely by condensation of amidines, by direct one-pot template synthesis from nitriles, by nucleophilic addition of amidines or related reagents to coordinated nitriles, by nucleophilic additions to dicyanamidate or hydrolytic conversion of triazines.