(MeZn)2(μ-ƞ2:ƞ2-N6Ph2) - A Powerful Starting Reagent for the Synthesis of Metal Hexazene Complexes

[(MeLDippZn)2(μ-η22-PhN6Ph)] (3), which was synthesized by reaction of MeLDipp2Zn2 with PhN3, reacts with two equivalents of Me2Zn to give [(MeZn)2(μ-η22-PhN6Ph)] (2). The reaction of 2 with pyridine gave [(MeZn)2(μ-η22-PhN6Ph)(Py)2] (4), while reactions with H-acidic ligands (MeLMesH, MeLPhH) occurred with elimination of methane and formation of [(MeLMesZn)2(μ-η22-PhN6Ph)] (1) and [(MeLPhZn)2(μ-η22-PhN6Ph)] (5). The reaction of 1 with two equivalents of MeLi yielded the heterobimetallic hexazene complex [(MeZn)(μ-η22-PhN6Ph)(Li)], which was found to undergo stepwise reaction with Me2AlCl to give [MeZn(μ-η22-PhN6Ph)AlMe2] and finally [(Me2Al)2(μ-η22-PhN6Ph)(thf)2] (6). Compounds 36 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.


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