Donor-stabilized germyl cations. Stable pentacoordinate germanium chloride [PhGe(OCH2CH2NMe2)2][Cl]
Donor-stabilized germyl cations. Stable pentacoordinate germanium chloride [PhGe(OCH2CH2NMe2)2][Cl]
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供体稳定的甲芽基阳离子。
DOI：
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发表时间：
2006
期刊：
影响因子：
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通讯作者：
M. Nechaev
中科院分区：
文献类型：
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作者：
V. Khrustalev;Ivan A. Portnyagin;I. Borisova;N. N. Zemlyansky;Yu. A. Ustynyuk;M. Antipin;M. Nechaev
制备了分子内配位的苯基双[N-(二甲氨基)乙氧基]氯化锗(1)，并通过溶液中的 1 H 和 13 C NMR 光谱以及晶体中的 X 射线衍射分析了其结构。化合物 1 在氢键供体溶剂（例如 CHCl 3 ）中倾向于电离，形成离子五配位形式 [PhGe(OCH 2 CH 2 NMe 2 ) 2 ][Cl] (1b)，而中性六配位形式 PhGe(OCH 2 CH 2 NMe 2 ) 2 Cl (la) 占主导地位。由CHCl 3 生长的晶体也代表形式1b。盐 1b 是第一种在环境条件下稳定的化合物，含有 [RGeX 2 ] + 类型的游离锗阳离子（R = Alk、Ar；X = 通过杂原子与锗原子键合的取代基：Hal、OR、NR 2 ），在高亲核氯离子存在的情况下，锗原子上没有大的取代基。
Intramolecularly coordinated phenylbis[N-(dimethylamino)ethoxy]germanium chloride (1) has been prepared, and its structure has been investigated by 1 H and 13 C NMR spectroscopy in solutions and by X-ray diffraction analysis in the crystal. Compound 1 tends to ionize in hydrogen-bond-donor solvents, such as CHCl 3 , with the formation of the ionic pentacoordinate form [PhGe(OCH 2 CH 2 NMe 2 ) 2 ][Cl] (1b) dominating over the neutral hexacoordinate form PhGe(OCH 2 CH 2 NMe 2 ) 2 Cl (la). Crystals grown from CHCl 3 also represent the form 1b. Salt 1b is the first compound stable under ambient conditions containing a free germanium cation of the type [RGeX 2 ] + (R = Alk, Ar; X = substituent bonded to the germanium atom by a heteroatom: Hal, OR, NR 2 ) without bulky substituents at the germanium atom in the presence of the highly nucleophilic chloride anion.