The electronic excited states of the iron(II) complex [Fe-II(tpy)(pyz-NHC)](2+) [tpy = 2,2':6',2 ''-terpyridine; pyz-NHC = 1,1'-bis(2,6-diisopropylphenyl)pyrazinyl-diimidazolium-2,2'-diylidene] and their relaxation pathways have been theoretically investigated. To this purpose, trajectory surface-hopping simulations within a linear vibronic coupling model including a 244-dimensional potential energy surface (PES) with 20 singlet and 20 triplet coupled states have been used. The simulations show that, after excitation to the lowest-energy absorption band of predominant metal-to-ligand charge-transfer character involving the tpy ligand, almost 80% of the population undergoes intersystem crossing to the triplet manifold in about 50 fs, while the remaining 20% decays through internal conversion to the electronic ground state in about 300 fs. The population transferred to the triplet states is found to deactivate into two different regions of the PESs, one where the static dipole moment is small and shows increased metal-centered character and another with a large static dipole moment, where the electron density is transferred from the tpy to pyz-NHC ligand. Coherent oscillations of 400 fs are observed between these two sets of triplet populations, until the mixture equilibrates to a ratio of 60:40. Finally, the importance of selecting suitable normal modes is highlighted-a choice that can be far from straightforward in transition-metal complexes with hundreds of degrees of freedom.