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Isolation and Structural Determination of a Hexacoordinated Antimony(V) Dication
Author(s) -
Sakabe Masato,
Sato Soichi
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202004659
Subject(s) - dication , chemistry , antimony , stibine , intramolecular force , crystallography , photochemistry , inorganic chemistry , molecule , stereochemistry , organic chemistry , arsine , phosphine , catalysis
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 ][SbCl 6 ] 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 ][SbCl 6 ] 2 exhibits remarkable thermal stability and the three ppy ligands on the antimony atom are shown to be magnetically inequivalent in the 1 H and 13 C NMR spectra. A hexacoordinated, meridional octahedral bonding geometry has been determined for [ 1 ][SbCl 6 ] 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 1 H 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.