Salts of the Dianions [Hg(12-X-closo-1-CB11H10)2]2– (X = I, C≡CH, C≡CFc, C≡CSiiPr3): Synthesis and Spectroscopic and Structural Characterization
Salts of the Dianions [Hg(12-X-closo-1-CB11H10)2]2– (X = I, C≡CH, C≡CFc, C≡CSiiPr3): Synthesis and Spectroscopic and Structural Characterization
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DOI：
10.1021/om5009956
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发表时间：
2015-01
期刊：
影响因子：
2.8
通讯作者：
Alexander Himmelspach;J. Warneke;Marius Schäfer;Michael Hailmann;M. Finze
中科院分区：
文献类型：
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作者：
Alexander Himmelspach;J. Warneke;Marius Schäfer;Michael Hailmann;M. Finze
合成了带双负电荷的汞（II）配合物[Hg（12-I-closo-1-CB 11 H 10）2]2-（1）、[Hg（12-HC Closo-1-CB 11 H 10）2]2-（2）、[Hg（12-FcC Closo-1-CB 11 H 10）2]2-（3）和[Hg（12-iPr 3SiC Closo-1-CB 11 H 10）2]2-（4）的铯盐或四乙基铵盐。炔基官能化簇的合成通过两种不同的路线进行。炔基部分要么是存在之前形成的汞（II）络合物或通过Pd催化的交叉偶联反应，使用Cs21作为起始材料引入。化合物的特征在于多核磁共振和振动光谱，质谱和元素分析。在（−）-ESI质谱实验中，通过碰撞诱导解离研究了二价阴离子1、2和3的气相反应。用X射线衍射法研究了Cs21·2 MeCN、Cs21·xMe 2CO（x = 2）、[Et 4 N]22·yEt 2CO（y = 4）和[Et 4 N]23的单晶。在Cs21·xMe 2CO（x ≠ 2）晶体中，二价阴离子和一半的Cs+阳离子形成一个六方堆积结构。
Cesium or tetraethylammonium salts of the doubly negatively charged mercury(II) complexes [Hg(12-I-closo-1-CB11H10)2]2– (1), [Hg(12-HC≡C-closo-1-CB11H10)2]2– (2), [Hg(12-FcC≡C-closo-1-CB11H10)2]2– (3), and [Hg(12-iPr3SiC≡C-closo-1-CB11H10)2]2– (4) were synthesized. The synthesis of the alkynyl-functionalized clusters was conducted via two different routes. The alkynyl moiety either was present before formation of the mercury(II) complex or was introduced via a Pd-catalyzed cross-coupling reaction using Cs21 as starting material. The compounds were characterized by multi-NMR and vibrational spectroscopy, mass spectrometry, and elemental analysis. Gas-phase reactions of the dianions 1, 2, and 3 were studied by collision-induced dissociation in (−)-ESI mass spectrometry experiments. Single crystals of Cs21·2MeCN, Cs21·xMe2CO (x ≈ 2), [Et4N]22·yEt2CO (y ≈ 4), and [Et4N]23 were studied by X-ray diffraction. In the crystals of Cs21·xMe2CO (x ≈ 2) the dianions and half of the Cs+ cations form a stacked hexagonal...