First evidence for the coordination of norbornadiene (nbd) and dicyclopentadiene (dcpd) with the main group metal Mg is provided by the crystal structures of adducts with cationic β-diketiminate (BDI) Mg complexes. While the dcpd complex is thermally stable, [(BDI)Mg+·nbd][B(C6F5)4-] shows slow room temperature retro-Diels-Alder decomposition to give a complex with the cation (BDI)Mg(C5H5)Mg(BDI)+.