In conclusion, this work highlights the significant influence ligand architecture can have on the coordination chemistry of dimagnesium complexes supported by dinucleating naphthyridine-based ligands. For the described reactivity of the dipp NDC and dipp DAMN ligands with Grignard reagents this influence is of steric nature, with the steric bulk surrounding the Mg 2 Cl 2 core differing markedly between the two ligands. This divergence is expressed in different coordination geometries around the Mg centres, which largely depend on the degree of coordinative saturation that is allowed by the steric bulk imposed by the dinucleating ligands. In contrast, the described reactivity of the dipp NDC and dipp DAMN ligands with dialkylmagnesium reagents highlights how subtle changes in ligand design can have a pronounced influence on the stability of the resulting Mg 2 Bu 2 complexes. Whereas dipp DAMN forms a well-defined, diamagnetic Mg 2 (n-Bu) 2 complex, the extended conjugated system of dipp NDC results in paramagnetic species that form upon Mg-C homolysis and subsequent radical reactivity. Collectively, these findings establish a framework for leveraging ligand design to tailor the reactivity of organomagnesium complexes, opening avenues for the development of novel organometallic transformations.