In this study we targeted aluminium hydrides as potential single source precursors for vapor phase deposition processes of Al metal, with the scope of improving the lack of thermal stability in existing Al complexes, through ligand stabilization. Three different ligand classes were chosen, namely small alkyl amines, dimethylaminopropyl and diamines. The significant impact of coordination sphere and ligand design on the complexes stability and intermolecular coordination behavior is demonstrated from comparative FTIR and NMR analyses. Thermal decomposition and rest mass analysis yielded metallic aluminium as the main decomposition product, indicating the potential for the targeted application as CVD precursor. This was further confirmed by DFT simulations, where in addition to the relaxed geometries of the complexes, bond dissociation energies were computed, giving insight into favored decomposition pathways. To assess the potential as a possible ALD precursor, reaction enthalpies for reactions with H2 and NH3 were calculated, revealing NH3 as the more reactive potential co-reactant for all three investigated compounds. With this study we aim to highlight the great potential of stabilized aluminium hydrides as a currently underestimated precursor class for vapor phase deposition processes, especially for the more sensitive material systems Al and AlN. Future work will focus on validating these exciting results in ALD process development for Al and AlN thin film deposition.