Two synthetic protocols, a salt metathesis reaction and a direct metalation, were developed for preparing 1,4-diaza-1,3-butadiene complexes of barium, strontium, and calcium, in which 1,4-diaza-1,3-butadiene serves as a dianionic or monoanionic ligand. A salt metathesis reaction of BaI 2 with the dipotassium salt of N,N′-bis(2,6-diisopropylphenyl)-1,4-diaza-1, 3-butadiene (1; abbreviated (Dip) 2DAD) afforded the iodide-bridged dinuclear complex [[K((Dip) 2DAD)(THF) 2][Ba(ν-I)(THF) 2]] 2 (2) bearing a dianionic ene-diamide ligand, while the reaction of MI 2 (M = Sr, Ca) with the dipotassium salt of 1 gave the mononuclear complexes [M((Dip) 2DAD)[THF] 4] (4, M = Sr; 5, M = Ca). A direct metalation reaction of barium powder with (Dip) 2DAD in the presence of iodine (10 mol%) afforded an iodide-bridged dinuclear complex, [Ba((Dip) 2DAD)(ν-I)(THF) 2] 2 (3), in which (Dip) 2DAD coordinates as a monoanionic ligand to the barium center, as was evident from the X-ray analysis and the EPR spectral data. The products from the direct metalation reaction of Sr and Ca powders with 1 in the presence of a catalytic amount of iodine (1 mol%) resulted in the formation of mononuclear complexes 4 and 5 bearing the dianionic ene-diamide DAD ligand. © 2012 American Chemical Society.