The detailed investigation of these Mn-containing complex has shown a much lower thermal stability and higher reactivity towards ambient conditions (oxygen and moisture) compared to other complexes. Interestingly the handling of all-nitrogen coordinated compounds showed major differences in comparison to the mixed coordinated compounds as these seem to be less reactive towards the ambient. Especially, the unique reactivity is not necessarily a bad precursor property. Not only these observations but also the general consideration in terms of thermal stability make theoretical investigations of these compounds valuable, as they finally can give even more hints for the appropriate usability as precursor for ALD and CVD. To get more detailed insights into that, DFT calculations were performed on these compounds and as starting point the corresponding molecule structures were calculated. While all-N coordinated compounds (I-VII) are modelled in the mononuclear and dinuclear form, given the magnetic moments found for the N/O coordinated compounds, ßI and ßII are modelled in the dinuclear form and ßIII and ßIV are modelled in the mononuclear form. The DFT calculated structure of compound (I-VII) and compound (ßI-ßIV) can be found in Figure , S9 and S10 respectively. The calculated Mn-N distances for compounds I-VII in the mononuclear form are in the range of 2.10 Å -2.17 Å, 2.13 Å -2.19 Å and 2.12 Å -2.19 Å for the amidinates (I,II), the formamidinates (III,IV) and guanidinates (V,VI,VII), respectively, Table . For the dinuclear form, compounds I-VII have similar Mn-N distances, ranging from 2.15 Å to 2.22 Å for the non-bridging ligands and 2.13 Å to 2.15 Å for bridging ligands, Table . A shorter metal-N bond suggests a higher stability, therefore, we expect the non-bridging ligands with longer Mn-N distances to be more reactive. Interestingly, for compound ßI and ßII, longer Mn-N bonds are calculated for non-bridging ligands (1.98 Å to 2.06 Å) compared to bridging ligands (1.89 Å to 2.05 Å) while the Mn-O bonds are shorter for the non-bridging ligands (1.93 Å to 1.95 Å) compared to bridging ligands (2.0 Å to 2.08 Å). For compound ßIII and ßIV calculated Mn-N are in the range of 2.12 Å to 2.16 Å and all Mn-O bonds are 2.02 Å, Table . In general, calculated Mn-N bonds of ß-ketoiminate components are shorter compared to those of all-N coordinated components, suggesting a higher stability of ß-ketoiminates. Another measure of stability is bond dissociation energy (loss of the first ligand moiety), which we calculated for all compounds, and these are listed in Table . The calculated bond dissociation energies of compounds I-VII were found to be higher for their mononuclear form compared to the dinuclear form, and this indicates a higher stability of these components as monomers. To explain this deviation from the experimental observations, it needs to be considered that only simple ligand cleavage reactions were considered for these calculations, while more complex reactions like de-insertion reactions were not considered. Interestingly, the bond dissociation energy of the Mn ß-ketoiminates are generally higher in comparison with the values of the all N-coordinated compounds, excluding compound ßII, for which a slightly lower bond dissociation energy is calculated. Calculated energetics show that more energy is needed to dissociate the ß-ketoiminates and indicate a higher stability of N/O coordinated compounds which is in accordance with the calculated geometries. Due to the proven promising thermal properties, compound IV and ßIII were used as model for chemical reaction simulations with O2. Therefore, an oxygen molecule was placed at a distance of 2.5 Å from the metal center of the corresponding molecules and optimized afterwards. The respective structural data are presented in the SI. For the case of compound IV, the Mn-N bonds to the non-bridging and bridging ligands of the dinuclear structure were considered separately.