The hexacoordinated antimony(V) dication [(ppy) Sb] ([1] ; ppy=2-(2-pyridyl)phenyl), stabilized by three intramolecular donor-acceptor interactions, has been isolated as its hexachloroantimonate salt [1][SbCl ] , prepared by the oxidative addition of chlorine to the neutral stibine [(ppy) Sb] (1), followed by the abstraction of chloride. Air-stable [1][SbCl ] exhibits remarkable thermal stability and the three ppy ligands on the antimony atom are shown to be magnetically inequivalent in the H and C NMR spectra. A hexacoordinated, meridional octahedral bonding geometry has been determined for [1][SbCl ] 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 NMR spectroscopy. The potential to generate dications by using a single-electron-transfer reagent has also been investigated. The dication [1] is the first [12-Sb-6] chemical species to have been structurally determined.
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View Article and Find Full Text PDFIsolation and Structural Determination of a Hexacoordinated Antimony(V) Dication.
Chemistry
March 2021
Department of Chemistry, Graduate School of Science, Tokyo Metropolitan University, 1-1 Minami-osawa, Hachioji, Tokyo, 1920397, Japan.
Invited for the cover of this issue are Masato Sakabe and Soichi Sato at Tokyo Metropolitan University. The image depicts the new hexacoordinated dicationic antimony species reported in this work. Read the full text of the article at 10.
View Article and Find Full Text PDFIsolation and Structural Determination of a Hexacoordinated Antimony(V) Dication.
Chemistry
March 2021
Department of Chemistry, Graduate School of Science, Tokyo Metropolitan University, 1-1 Minami-osawa, Hachioji, Tokyo, 1920397, Japan.
The hexacoordinated antimony(V) dication [(ppy) Sb] ([1] ; ppy=2-(2-pyridyl)phenyl), stabilized by three intramolecular donor-acceptor interactions, has been isolated as its hexachloroantimonate salt [1][SbCl ] , prepared by the oxidative addition of chlorine to the neutral stibine [(ppy) Sb] (1), followed by the abstraction of chloride. Air-stable [1][SbCl ] exhibits remarkable thermal stability and the three ppy ligands on the antimony atom are shown to be magnetically inequivalent in the H and C NMR spectra. A hexacoordinated, meridional octahedral bonding geometry has been determined for [1][SbCl ] by X-ray crystallographic analysis.
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