Further studies into the reactivity and coordination chemistry of [Ge9]4- Zintl ions. The indium-containing anions [In(Ge9)2]5-, [(Ge9)2In(C6H5)]4- and [Ge9{In(C6H5)3}2]4-
Further studies into the reactivity and coordination chemistry of [Ge9]4- Zintl ions. The indium-containing anions [In(Ge9)2]5-, [(Ge9)2In(C6H5)]4- and [Ge9{In(C6H5)3}2]4-
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DOI：
10.1016/j.jorganchem.2012.05.037
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发表时间：
2012-12-15
影响因子：
2.3
通讯作者：
Goicoechea, Jose M.
中科院分区：
文献类型：
--
作者：
Hansen, David F.;Zhou, Binbin;Goicoechea, Jose M.
K_4Ge_9的乙二胺溶液与三苯基铟反应生成了三个新的Zintl离子：[In（Ge-9）（2）]（5-）（1），[（Ge-9）（2）In（C_6H_5）]（4-）（2），[Ge-9{In（C_6H_5）（3）}（2）}]（4-）（3）。物种1展示了由两个九原子锗笼配位的铟金属原子，所述锗笼以η（3）-模式与中心金属键合。两个簇的“交错”排列赋予铟金属中心八面体配位几何形状。物种2显示出围绕铟原子的三角平面配位，其中[In（C6 H5）]（2+）部分充当[Ge-9-Ge-9]（6-）二聚体的两半之间的桥。最后，物种3是由一个[Ge-9]（4-）三角形Zintl离子作为刘易斯碱两个在（C6 H5）（3）部分。所有三种阴离子在固态下通过单晶X射线衍射分别在[K（2，2，2-crypt）]（5）[1]中心点2 en、[K（2，2，2-crypt）]（4）[2]中心点3 tol和[K（2，2，2-crypt）]（4）[3]中进行表征。溶液中阴离子的存在，证实了电喷雾质谱。DFT水平的计算也进行了所有的簇阴离子。(C)2012年爱思唯尔B。版权所有© 2016
Reactions between ethylenediamine solutions of K4Ge9 and triphenylindium yielded three novel Zintl ions, [In(Ge-9)(2)](5-) (1), [(Ge-9)(2)In(C6H5)](4-) (2), and [Ge-9{In(C6H5)(3)}(2)}](4-) (3). Species 1 exhibits an indium metal atom coordinated by two nine-atom germanium cages which bond to the central metal in an eta(3)-mode. The "staggered" arrangement of the two clusters confers the indium metal centre an octahedral coordination geometry. Species 2 displays trigonal planar coordination around the indium atom with an [In(C6H5)](2+) moiety acting as a bridge between the two halves of a [Ge-9-Ge-9](6-) dimer. Finally, species 3 is composed of a [Ge-9](4-) deltahedral Zintl ion acting as a Lewis base to two In(C6H5)(3) moieties. All three anions were characterized in the solid-state by single-crystal X-ray diffraction in [K(2,2,2-crypt)](5)[1]center dot 2en, [K(2,2,2-crypt)](4)[2]center dot 3tol and [K(2,2,2-crypt)](4)[3], respectively. The existence of the anions in solution was confirmed by electrospray mass-spectrometry. DFT level calculations were also conducted on all of the cluster anions. (C) 2012 Elsevier B. V. All rights reserved.