Photoexcitation of [FeII(2,2'-bipyridine)3]2+ induces a subpicosecond spin crossover transformation from a low-spin singlet to a high-spin quintet state. The mechanism involves metal-centered (MC) and metal-ligand charge transfer (MLCT) triplet intermediates, but their individual contributions to this efficient intersystem crossing have been object of debate. Employing quantum wavepacket dynamics, we show that MC triplets are catalyzing the transfer to the high-spin state. This photochemical pathway is made possible thanks to bipyridine stretching vibrations, facilitating the conversion between the MLCT bands to such MC triplets. We show that the lifetime of the MLCT states can be increased to tens of picoseconds by breaking the conjugation between pyridine units, which increases the energetic gap between MLCT and MC states. This opens the route for the design of new chelating ligands inducing long-lived MLCT states in iron complexes.