The zinc hexazene complex (Me)L2Zn2(μ-1,6-Ph2-N6) 1 ((Me)L = HC[C(Me)N(2,4,6-Me3C6H2)]2) is a suitable hexazene transfer reagent in reactions with main group metal and transition metal complexes containing M-Me units. The reactions proceed with elimination of (Me)LZnMe and the resulting complexes were characterized by NMR and IR spectroscopy and single crystal X-ray diffraction (5, 8). Quantum chemical calculations were performed to investigate the electronic structure of 5' and 8' in more detail and to identify the absorption bands of the hexazene unit.