The synthesis of two different types of bis(N,N',N'-substituted 1,2-ethanediamine)s, bridged either through the secondary (type 1) or tertiary (type 2) amine groups is reported. Selected protio-ligands have been applied in subsequent metallation reactions using aluminium, magnesium, tin, and zinc sources allowing to isolate five mononuclear and eight dinuclear complexes. All complexes have been fully characterized and their solid-state structures have been studied by means of single-crystal X-ray diffraction analysis. Nine of the 13 complexes carry reactive alkyl, amide or hydride groups, which indicates their potential as catalysts or supports for (transition) metals.