Remarkable Dinitrogen Activation and Cleavage by the Gd Dimer: From Dinitrogen Complexes to Ring and Cage Nitrides

Building up from scratch: The Gd2 molecule reacts with N2 in solid argon to form a homoleptic dinuclear dinitrogen complex containing a drastically activated side-on and end-on bonded N2 ligand (see scheme; Gd orange, N blue). The complex rearranges to a planar cyclic [Gd(μ-N)2Gd] isomer with a completely cleaved NN bond, which further dimerizes to form a cubic [Gd4N4] cluster, a building block for (GdN)x nanoparticles.