[(^MeL^DippZn)₂(μ-η²:η²-PhN₆Ph)] (3), which was synthesized by reaction of ^MeL^Dipp₂Zn₂ with PhN₃, reacts with two equivalents of Me₂Zn to give [(MeZn)₂(μ-η²:η²-PhN₆Ph)] (2). The reaction of 2 with pyridine gave [(MeZn)₂(μ-η²:η²-PhN₆Ph)(Py)₂] (4), while reactions with H-acidic ligands (^MeL^MesH, ^MeL^PhH) occurred with elimination of methane and formation of [(^MeL^MesZn)₂(μ-η²:η²-PhN₆Ph)] (1) and [(^MeL^PhZn)₂(μ-η²:η²-PhN₆Ph)] (5). The reaction of 1 with two equivalents of MeLi yielded the heterobimetallic hexazene complex [(MeZn)(μ-η²:η²-PhN₆Ph)(Li)], which was found to undergo stepwise reaction with Me₂AlCl to give [MeZn(μ-η²:η²-PhN₆Ph)AlMe₂] and finally [(Me₂Al)₂(μ-η²:η²-PhN₆Ph)(thf)₂] (6). Compounds 3–6 were characterized by elemental analysis, NMR spectroscopy, and single-crystal X-ray diffraction. Quantum chemical calculations were performed in order to investigate the electronic structure of 4′ and 6′ in more detail and to identify the absorption bands of the hexazene unit.