Metalation of 1,3-bis(2,4,6-trimethylphenyl)triazene (1) with KH, Mg(nBu)2, and [(L)2Ae{N(SiMe3)2}2] (Ae/L = Ca/thf, Sr/dme) yields the dinuclear complexes [(thf)2K{μ-N3(Mes)2}]2 (2a) and [(dme)K{μ-N3(Mes)2}]2 (2b) as well as mononuclear [(thf)2Mg{N3(Mes)2}2] (3a), [(tmeda)Mg(nBu){N3(Mes)2}] (3b), [(thf)2Ca{N3(Mes)2}2] (4), and [(tmeda)Sr{N3(Mes)2}2] (5), respectively, with high yields depending on applied stoichiometry and donor solvent [tetrahydrofuran (THF), 1,2-dimethoxyethane (DME), 1,2-bis(dimethylamino)ethane (TMEDA)]. The 1,3-bis(2,4,6-trimethylphenyl)triazene (1) forms a strand-like structure in the solid state, stabilized by N–H⋯N hydrogen bridges and intermolecular π-stacking of the mesityl groups. The 1,3-bis(2,4,6-trimethylphenyl)triazenide anions of the s-block metal complexes show charge delocalization within the triazaallylic systems and act as bidentate chelate ligands.
