Magnesium aluminate complexes find use as electrolytes in rechargeable batteries. However, very little is known about their exact constitution when dissolved in solution, with mono-, di- and trinuclear complexes all implicated at various times by other research groups [(MgxCl2x-1), x = 1, 2, 3]. This project has proven that the aggregation state can be controlled by carefully selecting the Lewis donor (the neutral ligand which protects reactive magnesium) according to its size profile. A reproducible synthetic protocol for these magnesium aluminates has been developed, giving access to a large family of with a variety of different bulky secondary amides. These species are very difficult to study in solution, however with our large library of relevant complexes now prepared, we have displayed the applicability of electrospray ionization mass spectrometry as a tool for studying the solution make-up of these materials, and have made some preliminary investigations into the use of Raman spectroscopy.