Halometallate complexes of germanium(II) and (IV): probing the role of cation, oxidation state and halide on the structural and electrochemical properties.
Halometallate complexes of germanium(II) and (IV): probing the role of cation, oxidation state and halide on the structural and electrochemical properties.
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DOI：
10.1002/chem.201400179
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发表时间：
2014-04-22
影响因子：
4.3
通讯作者：
Reid, Gillian
中科院分区：
文献类型：
--
作者：
Bartlett, Philip N.;Cummings, Charles Y.;Levason, William;Pugh, David;Reid, Gillian
已合成并完全合成了GeIV氯金属酸盐配合物[EMIM]2[GeCl6]、[EDMIM]2[GeCl6]和[PYRR]2[GeCl6]（EMIM=1-乙基-3-甲基咪唑鎓；EDMIM=2,3-二甲基-1-乙基咪唑鎓；PYRR=N-丁基-N-甲基吡咯烷鎓） 具有特征；前两个也是通过单晶 X 射线衍射得到的。咪唑鎓氯金属盐表现出显着的 C–H⋅⋅⋅Cl 氢键，从而在固态下形成扩展的超分子组装体。溶液 1H NMR 数据也显示出阳离子-阴离子缔合。报道了 GeII 卤金属盐 [EMIM][GeX3] (X=Cl, Br, I) 和 [PYRR][GeCl3] 的合成和表征，包括同系咪唑鎓盐系列的单晶 X 射线分析。在这些复合物中，分子间相互作用在固态下要弱得多，并且它们在溶液中似乎没有显着关联。 GeIV 物质在 CH2Cl2 溶液中的循环伏安实验显示出两种不同的、不可逆的还原波，归因于 GeIV–GeII 和 GeII–Ge0，而 GeII 物质则表现出一种不可逆的还原波。尽管将前体的氧化态从 GeIV 改变为 GeII 确实会产生影响，但改变阳离子不会影响 GeII-Ge0 还原的潜力；对于给定的阳离子，[GeCl3]−盐的还原发生在较低的阴极电位下。卤化物共配体的性质也对 GeII-Ge0 对的还原电位有显着影响，因此当卤化物 (X) 变为 Cl→Br→I 时，[GeX3]− 盐的还原电位显着降低阴极性。
The GeIV chlorometallate complexes, [EMIM]2[GeCl6], [EDMIM]2[GeCl6] and [PYRR]2[GeCl6] (EMIM=1-ethyl-3-methylimidazolium; EDMIM=2,3-dimethyl-1-ethylimidazolium; PYRR=N-butyl-N-methylpyrrolidinium) have been synthesised and fully characterised; the first two also by single-crystal X-ray diffraction. The imidazolium chlorometallates exhibited significant C–H⋅⋅⋅Cl hydrogen bonds, resulting in extended supramolecular assemblies in the solid state. Solution 1H NMR data also showed cation–anion association. The synthesis and characterisation of GeII halometallate salts [EMIM][GeX3] (X=Cl, Br, I) and [PYRR][GeCl3], including single-crystal X-ray analyses for the homologous series of imidazolium salts, are reported. In these complexes, the intermolecular interactions are much weaker in the solid state and they appear not to be significantly associated in solution. Cyclic-voltammetry experiments on the GeIV species in CH2Cl2 solution showed two distinct, irreversible reduction waves attributed to GeIV–GeII and GeII–Ge0, whereas the GeII species exhibited one irreversible reduction wave. The potential for the GeII–Ge0 reduction was unaffected by changing the cation, although altering the oxidation state of the precursor from GeIV to GeII does have an effect; for a given cation, reduction from the [GeCl3]− salts occurred at a less cathodic potential. The nature of the halide co-ligand also has a marked influence on the reduction potential for the GeII–Ge0 couple, such that the reduction potentials for the [GeX3]− salts become significantly less cathodic when the halide (X) is changed Cl→Br→I.
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影响因子：
3.3
作者：
Al-Salman, R.;El Abedin, S. Zein;Endres, F.
通讯作者：
Endres, F.
DOI：
10.1039/dt9910002777
发表时间：
1991-10-01
期刊：
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS
影响因子：
--
作者：
CHAMPNESS, NR;LEVASON, W;WEBSTER, M
通讯作者：
WEBSTER, M
DOI：
10.1039/jr9630002189
发表时间：
1963-01-01
期刊：
JOURNAL OF THE CHEMICAL SOCIETY
影响因子：
--
作者：
ADAMS, DM;GERRATT, J;CHATT, J
通讯作者：
CHATT, J
影响因子：
2.3
作者：
Cheng, Fei;Davis, Martin F.;Zhang, Wenjian
通讯作者：
Zhang, Wenjian
影响因子：
3.3
作者：
Endres, F;El Abedin, SZ
通讯作者：
El Abedin, SZ