β-diketiminate coordinated magnesium(I) compounds, [{(ArNacnac)Mg}2] (ArNacnac = [(ArNCMe)2CH]- (Ar = 2,6-diisopropylphenyl (Dip) or mesityl (Mes)), have been utilized as reducing agents in reactions with the redox active 1,4-diazabutadiene, (ButNCH)2 (ButDAB) and 2,2′-bipyrine (bipy). These reactions led to one-electron reductions of the unsaturated substrate and formation of the highly colored radical complexes, [(ArNacnac) Mg(ButDAB.)] and [(MesNacnac)Mg(bipy.)(bipy)]. The X-ray crystal structures of the compounds reveal each to possess one singly reduced ButDAB or bipy ligand. © 2020 Yuvaraj and Jones.