期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 27, 期 18, 页码 5658-5665出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202004659
关键词
antimony; density functional calculations; main group elements; pnictogens; polycations; structure elucidation
资金
- JSPS KAKENHI [24550060]
- Grants-in-Aid for Scientific Research [24550060] Funding Source: KAKEN
The hexacoordinated antimony(V) dication has been successfully isolated and shown to exhibit remarkable thermal stability and magnetically inequivalent ppy ligands. X-ray crystallographic analysis confirmed its hexacoordination, while theoretical calculations investigated the preferential generation of the meridional form.
The hexacoordinated antimony(V) dication [(ppy)(3)Sb](2+) ([1](2+); ppy=2-(2-pyridyl)phenyl), stabilized by three intramolecular donor-acceptor interactions, has been isolated as its hexachloroantimonate salt [1][SbCl6](2), prepared by the oxidative addition of chlorine to the neutral stibine [(ppy)(3)Sb] (1), followed by the abstraction of chloride. Air-stable [1][SbCl6](2) exhibits remarkable thermal stability and the three ppy ligands on the antimony atom are shown to be magnetically inequivalent in the H-1 and C-13 NMR spectra. A hexacoordinated, meridional octahedral bonding geometry has been determined for [1][SbCl6](2) by X-ray crystallographic analysis. Theoretical calculations were performed to investigate why the meridional form was generated preferentially over the facial form. In addition, the dynamics of the ppy ligands were investigated by variable-temperature H-1 NMR spectroscopy. The potential to generate dications by using a single-electron-transfer reagent has also been investigated. The dication [1](2+) is the first [12-Sb-6](2+) chemical species to have been structurally determined.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据