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首页> 外文期刊>Zeitschrift fur Anorganische und Allgemeine Chemie >Chiral gallium and indium alkoxometalates [German]
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Chiral gallium and indium alkoxometalates [German]

机译:手性镓和铟的金属氧酸盐[德国]

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Li-2(S)-BINOLate ((S)-BINOL = (S)-(-)-2,2'-Dihydroxy-1,1'-binaphthyl) generated by dilithiation of (S)-BINOL with two equivalents (BuLi)-Bu-n was reacted with GaCl3 und InCl3 in THF to the alkoxometalates [{Li(THF)(2)}{Li(THF)}(2){Ga((S)-BINOLate)(3)}] (1) and [{Li(THF)(2)}(2){Li(THF)}{In((S)-BINolate)(3))] . [{Li(THF)(2)}{Li(THF)}(2){In((S)-BINOLate)(3)}](2) (3), respectively. 1 and 3 crystallize from THF/toluene mixtures as 1 . 2 toluene and 3 . 8 toluene. The treatment of PhCH2GaCl2 with Li-2(S)-BINOLate in THF under reflux, followed by recrystallization of the product from DME gives the gallate [{Li(DME)}(3){Ga((S)-BINOLate)(3)}] . 1.5 THF (2 . 1.5 THF). 1-3 were characterized by NMR, IR and MS techniques. In addition, 1 . 2 toluene, 2 . 1.5 THF and 3 . 8 toluene were investigated by X-ray structure analyses. According to them, a distorted octahedral coordination sphere around the group 13 metal was formed, built-up by three BINOLate ligands. The three Li+ counter ions act as bridging units by metal-oxygen coordination. The coordination sphere of the Li+ ions was completed, depending on the available space, by one or two THF ligands (1 . 2 toluene, 3 . 8 toluene) and one DME ligand (2 . 1.5 THF), respectively. The sterical dominance of the BINOLate ligands can be shown by the almost square-planar coordination of the Li+ ions in 2 . 1.5 THF giving a small twisting angle of only 17 degrees. [References: 32]
机译:Li-2(S)-BINOLate((S)-BINOL =(S)-(-)-2,2'-Dihydroxy-1,1'-binaphthyl)由(S)-BINOL的二等价二甲酰化生成( BuLi)-Bu-n与GaCl3和InCl3在THF中反应生成烷氧基金属盐[{Li(THF)(2)} {Li(THF)}(2){Ga((S)-BINOLate)(3)}] (1)和[{Li(THF)(2)}(2){Li(THF)} {In((S)-BINolate)(3))]。 [{Li(THF)(2)} {Li(THF)}(2){In((S)-BINOLate)(3)}](2)(3)。 1和3从THF /甲苯混合物中以1结晶。 2甲苯和3。 8甲苯。用THF中的Li-2(S)-BINOLate在THF中回流处理PhCH2GaCl2,然后从DME中重结晶生成没食子酸酯[{Li(DME)}(3){Ga((S)-BINOLate)(3 )}]。 1.5 THF(2. 1.5 THF)。通过NMR,IR和MS技术表征1-3。另外,1。 2甲苯2。 1.5 THF和3。通过X射线结构分析研究了8种甲苯。据他们说,在第13组金属周围形成了一个扭曲的八面体配位球,由三个BINOLate配体建立。三个Li +抗衡离子通过金属-氧配位充当桥接单元。根据可用空间,分别通过一个或两个TH​​F配体(1.2甲苯,3.8甲苯)和一个DME配体(2. 1.5 THF)完成Li +离子的配位球。 BINOLate配体的空间优势可以通过2中Li +离子的几乎正方形平面配位来显示。 1.5 THF,扭转角仅为17度。 [参考:32]

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