Tuning the photophysical properties of iron-based transition-metal complexes is crucial for their employment as photosensitizers in solar energy conversion. For the optimization of these new complexes, a detailed understanding of the excited-state deactivation paths is necessary. Here, we report femtosecond transient mid-IR spectroscopy data on a recently developed octahedral ligand-field enhancing [Fe(dqp)$_2$]$^{2+}$ (C1) complex with dqp = 2,6-diquinolylpyridine and prototypical [Fe(bpy)$_3$]$^{2+}$ (C0). By combining mid-IR spectroscopy with quantum chemical DFT calculations, we propose a method for disentangling the $^5$Q$_1$ and $^3$T$_1$ multiplicities of the long-lived metal-centered (MC) states, applicable to a variety of metal–organic iron complexes. Our results for C0 align well with the established assignment toward the $^5$Q$_1$, validating our approach. For C1, we find that deactivation of the initially excited metal-to-ligand charge-transfer state leads to a population of a long-lived MC$^5$Q1 state. Analysis of transient changes in the mid-IR shows an ultrafast sub 200 fs rearrangement of ligand geometry for both complexes, accompanying the MLCT → MC deactivation. This confirms that the flexibility in the ligand sphere supports the stabilization of high spin states and plays a crucial role in the MLCT lifetime of metal–organic iron complexes.