Kalden Diana, Krieck Sven, Görls Helmar, Westerhausen Matthias
Institute of Inorganic and Analytical Chemistry, Friedrich Schiller University, Humboldstrasse 8, D-07743 Jena, Germany.
Dalton Trans. 2015 May 7;44(17):8089-99. doi: 10.1039/c5dt00595g.
Metalation of 1,3-bis(2,4,6-trimethylphenyl)triazene () 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 () and [(dme)K{μ-N3(Mes)2}]2 () as well as mononuclear [(thf)2Mg{N3(Mes)2}2] (), [(tmeda)Mg(nBu){N3(Mes)2}] (), [(thf)2Ca{N3(Mes)2}2] (), and [(tmeda)Sr{N3(Mes)2}2] (), 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 () forms a strand-like structure in the solid state, stabilized by N-HN 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.
用KH、Mg(nBu)₂和[(L)₂Ae{N(SiMe₃)₂}₂](Ae/L = Ca/thf,Sr/dme)对1,3-双(2,4,6-三甲基苯基)三氮烯( )进行金属化反应,分别高产率地得到双核配合物[(thf)₂K{μ-N₃(Mes)₂}]₂( )和[(dme)K{μ-N₃(Mes)₂}]₂( )以及单核配合物[(thf)₂Mg{N₃(Mes)₂}]( )、[(tmeda)Mg(nBu){N₃(Mes)₂}]( )、[(thf)₂Ca{N₃(Mes)₂}]( )和[(tmeda)Sr{N₃(Mes)₂}]( ),产率高低取决于所采用的化学计量比和给体溶剂[四氢呋喃(THF)、1,2-二甲氧基乙烷(DME)、1,2-双(二甲氨基)乙烷(TMEDA)]。1,3-双(2,4,6-三甲基苯基)三氮烯( )在固态中形成链状结构,通过N-HN氢键和均三甲苯基基团的分子间π堆积得以稳定。s区金属配合物中的1,3-双(2,4,6-三甲基苯基)三氮烯阴离子在三氮烯丙基体系内表现出电荷离域,并作为双齿螯合配体。