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Rare examples of trinuclear [Ni–N2–M–N2–Ni] core (M = Ca, Mg) with linear bridged dinitrogen ligands are reported in this work. The reduction of [iPr2NN]Ni(μ-Br)2Li(thf)2 (1) (iPr2NN = 2,4-bis-(2,6-diisopropylphenylimido)pentyl) with elemental Mg or Ca in THF under an atmosphere of dinitrogen yields the complex {iPr2NNNi(μ-N2)}2M (thf)4 (M = Mg, complex 2 and M = Ca, complex 3). The bridging end-on (μ-N2)2M(thf)4 moiety connects the two [iPr2NNNi]− nickelate fragments. A combination of X-ray crystallography, solution and solid-state spectroscopy have been applied to characterize complexes 2 and 3, and DFT studies have been used to help explain the bonding and electronic structure in these unique Ni–N2–Mg and Ni–N2–Ca complexes. [ABSTRACT FROM AUTHOR]