超强低价β-二偏二亚基镓(I)络合物的合成、结构和反应活性

Tim Richter, Stefan Thum, Oliver Townrow, Michael Wiesinger, Jens Langer, Sjoerd Harder
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引用次数: 0

摘要

在甲苯中用 KC8 还原 (DIPePBDI)GaI2 (1),得到了一种带有超强 b-二乙酰亚氨基配体 DIPePBDI 的低价 GaI 复合物(HC[C(Me)N-DIPeP]2,DIPeP = 2,6-C(H)Et2-苯基)。考虑到(BDI)GaI 和类似的(BDI)AlI 复合物容易分解,而且一般只能以较低的产率(20-40%)获得,(DIPePBDI)GaI (2) 的定量形成非常引人注目,这无疑与它即使在回流甲苯中也具有出色的热稳定性有关。虽然 2 中的低价金属中心受到了超强的 DIPePBDI 配体的立体保护,但它很容易被 N2O 氧化,生成中间体 (DIPePBDI)Ga=O,该中间体很容易通过从骨架 Me 取代基中抽取一个质子而分解。与三甲基硅叠氮反应得到中间体亚胺络合物 (DIPePBDI)Ga=N(SiMe3)2,与第二个当量的 Me3SiN3 反应生成叠氮/亚胺络合物 (DIPePBDI)GaN3[N(SiMe3)2] (4) 和四氮唑络合物 (DIPePBDI)Ga[N4(SiMe3)2] (5) 的混合物,比例为 1:2。叠氮/氨基复合物 4 可以从结构上确定其特征,而四氮唑复合物 5 则是通过核磁共振光谱确定的。对 (DIPePBDI)GaI (2) 及其反应产物的 DFT 计算补充了这项研究。
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Synthesis, structure, and reactivity of a superbulky low‐valentbeta‑diketiminate Ga(I) complex
A low‐valent GaI complex with the superbulky b‐diketiminate ligand DIPePBDI (HC[C(Me)N‐DIPeP]2, DIPeP = 2,6‐C(H)Et2‐phenyl)) was obtained by reduction of (DIPePBDI)GaI2 (1) with KC8 in toluene. Considering that (BDI)GaI and analogue (BDI)AlI complexes are prone to decomposition and can generally only be obtained in low yields (20‐40%), the quantitative formation of (DIPePBDI)GaI (2) is remarkable and no doubt related to its excellent thermal stability even in refluxing toluene. Although the low‐valent metal center in 2 is sterically protected by the superbulky DIPePBDI ligand, it is readily oxidized by N2O to give intermediate (DIPePBDI)Ga=O which readily decomposed by abstracting a proton from the backbone Me‐substituent. Reaction with trimethylsilyl azide gave an intermediate imido complex (DIPePBDI)Ga=N(SiMe3)2 which reacted with a second equivalent of Me3SiN3 to a mixture of an azide/amido complex (DIPePBDI)GaN3[N(SiMe3)2] (4) and a tetrazagallole complex (DIPePBDI)Ga[N4(SiMe3)2] (5) in a 1:2 ratio. Whereas the azide/amido complex 4 could be structurally characterised, the tetraazagallole complex 5 was identified by NMR spectroscopy. DFT calculations on (DIPePBDI)GaI (2) and its reaction products complement this study.
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