Several Lewis base adducts of the synthetically important lithium tris(n-butyl)magnesiate LiMg((n)Bu)3 have been prepared and structurally characterised. The complexes were prepared by a co-complexation approach i.e., by combining the monometallic (n)BuLi and (n)Bu2Mg reagents in hydrocarbon solution before adding a molar equivalent of a donor molecule (a bidentate amine, tridentate amine or cyclic ether). The lithium magnesiates all adopt variants of the "Weiss motif" structure, i.e., contacted ion pair dimers with a linear arrangement and metals connected by butyl anions, where tetrahedral magnesium ions are in the central positions and the lithiums occupy the outer region, solvated by a neutral Lewis donor [(donor)Li(μ-(n)Bu)2Mg(μ-(n)Bu)2Mg(μ-(n)Bu)2Li(donor)]. When TMPDA, PMDETA or (R,R)-TMCDA [TMPDA = N,N,N'N'-tetramethylpropanediamine; PMDETA = N,N,N',N'',N''-pentamethyldiethylenetriamine; and (R,R)-TMCDA = (R,R)-N,N,N',N'-tetramethylcyclohexane-1,2-diamine], are employed, dimeric tetranuclear lithium magnesiates are produced. Due to the tridentate nature of the ligand, the PMDETA-containing structure (2) has an unusual 'open'-motif. When TMEDA (TMEDA = N,N,N',N'-tetramethylethylenediamine) is employed, a n-butoxide-containing complex [(TMEDA)Li(μ-(n)Bu)(μ-O(n)Bu)Mg2((n)Bu)2(μ-(n)Bu)(μ-O(n)Bu)Li(donor)] has been serendipitously prepared and adopts a ladder conformation which is commonly observed in lithium amide chemistry. This complex has also been prepared using a rational methodology. When 1,4-dioxane is employed, the donor stitches together a polymeric array of tetranuclear dimeric units (6). The hydrocarbon solution structures of the compounds have been characterised by (1)H, (7)Li, (13)C NMR spectroscopy; 2 has been studied by variable temperature and DOSY NMR.