A series of titanium m2-nitrido complexes supported by the triamidoamine ligand Xy-N3N (Xy-N3N = {(3,5-Me2C6H3)NCH2CH2}3N3–) is reported. The titanium azido complex [(Xy-N3N)TiN3] (1-N3), prepared by salt metathesis of the chloride complex [(Xy-N3N)TiCl] (1-Cl) with NaN3, reacted with lithium metal or with alkali metal naphthalenides (alkali metal M = Na, K, and Rb) in THF to give the corresponding dinuclear m2-nitrido complexes M[(Xy-N3N)Ti=N-Ti(Xy-N3N)] (2-M; M = Li, Na, K, Rb). Single crystal X-ray diffraction studies of 2-Li, 2-Na, and 2-K revealed alkali metal dependent structures in the solid state. While 2-Li and 2-K contain a m2-nitrido ligand with a linear Ti–N–Ti core, 2-Na includes a m3-nitrido ligand as part of a T-shape Ti2NaN fragment with the sodium cation weekly coordinated to the nitrido nitrogen atom. When the synthesis of the nitrido complexes was carried out in the presence of excess alkali metals, selective decomposition of the nitrido complexes was observed affording some intractable titanium species along with the trialkali metal salts [M3(Xy-N3N)] (3-M) (M = Li, Na, K, and Rb). These salts were also prepared by deprotonation of (Xy-N3N)H3 with the corresponding alkali metal hexamethyldisilazide and characterized by multinuclear NMR spectroscopy as well as single crystal X-ray diffraction.

中文翻译：

---

含有线性 Ti-N-Ti 核和二配位氮化配体的桥接钛氮化配合物


报道了一系列由三酰胺胺配体 Xy-N3N (Xy-N3N = {(3,5-Me2C6H3)NCH2CH2}3N3–) 支撑的钛 m2-硝基配合物。钛叠氮络合物[(Xy-N3N)TiN3](1-N3)，由氯化物络合物[(Xy-N3N)TiCl](1-Cl)与NaN3进行盐复分解，与锂金属或碱金属反应制备萘化合物（碱金属 M = Na、K 和 Rb）在 THF 中得到相应的双核 m2-氮化物配合物 M[(Xy-N3N)Ti=N-Ti(Xy-N3N)] (2-M; M = Li 、Na、K、Rb）。 2-Li、2-Na 和 2-K 的单晶 X 射线衍射研究揭示了固态的碱金属依赖性结构。虽然 2-Li 和 2-K 含有一个带有线性 Ti-N-Ti 核心的 m2-氮化物配体，但 2-Na 包含一个 m3-氮化物配体作为 T 形 Ti2NaN 片段的一部分，钠阳离子每周与硝基氮原子。当在过量碱金属存在下进行氮化配合物的合成时，观察到氮化配合物的选择性分解，提供一些难以处理的钛物质以及三碱金属盐[M3(Xy-N3N)] (3-M) （M = Li、Na、K 和 Rb）。这些盐也通过 (Xy-N3N)H3 用相应的碱金属六甲基二硅氮化物去质子化来制备，并通过多核 NMR 光谱以及单晶 X 射线衍射进行表征。