Here, we assessed the performance of optimally-tuned range-separated DFT for a prototypical iron compound, [Fe(cpmp) 2 ] 2+ that, having push-pull ligands, exhibits increased lifetime of the MLCT states compared to simple iron polypyridyl complexes such as [Fe(bpy) 3 ] 2+ . We systematically employed different tuning schemes including "classical" ground-state fundamental gap tuning, ionization potential tuning in the triplet and quintet excited states, electron affinity tuning targeting metal-localized σ * orbitals, and the so-called triplet tuning. We found that the range-separation parameters strongly influence vertical and adiabatic excitation energies and importantly also the nature of the lowest excited states. Thus, an unambiguous choice of the tuning parameters for such molecules is not straitghforward. Aided by a comparison with the experimental absorption spectra and CASPT2 calculations, we found two suitable sets of range-separation parameters that were subsequently used for excited state dynamics simulations. Using the set of optimal parameters from the ∆SCF method (set A) for dynamical simulations results in the population of MLCT states that are stable within our 2 ps simulation time. This is in contrast to the TAS experiments , that show the depopulation of MLCT states within 200 fs. Using the set which is in agreement with multi-reference CASPT2 calculations (set B) leads to relaxation processes both within the singlet and triplet manifolds. The participating electronic states in this deactivation mechanism show pronounced MC character. Throughout the deactivation -and even upon reaching the hot S * 0 state -the system stays in regions of high-density of states, suggesting the possibility for further transfer into quintet states. We thus conclude that only set B, in agreement with multireference calculations, can describe the electronic states of [Fe(cpmp) 2 ] 2+ well.