A suite of late first row transition metal complexes has been synthesized using a monoanionic nitrogen donor β-diketiminate ligand with quinolyl pendant arms, BDI QQ H (1). BDI QQ NiOTf (2), BDI QQ CuCl (4), BDI QQ ZnCl (5) were prepared from the reaction of 1 with Ni(OTf) 2 , CuCl 2 ·2H 2 O and ZnCl 2 , respectively. BDI QQ NiCl (3) was synthesized from an anion exchange of 2 with n Bu 4 NCl. Reaction of 1 and CoI 2 afforded the unexpected [(BDI QQ ) 2 Co] + I − (6). Through density functional theory (DFT) calculations, ligand geometries in BDI QQ complexes were investigated and it was found that smaller ionic radius and higher charge destabilize 1:1 metal–ligand complexes relative to alternative 1:2 complexes like 6 owing to significant conformational strain in 1:1 complexes involving metals with small ionic radii. Synthesis and characterization of these complexes, including crystal structures of 4 and 5, are reported, in addition to the results of DFT calculations.