Organoantimony Dihydroperoxides : Synthesis, Crystal Structures, and Hydrogen Bonding Networks

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review

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Author(s)

  • Pavel A. Egorov
  • Dmitry A. Grishanov
  • Alexander G. Medvedev
  • Andrei V. Churakov
  • Alexey A. Mikhaylov
  • Roman V. Ottenbacher
  • Konstantin P. Bryliakov
  • Ovadia Lev
  • Petr V. Prikhodchenko

Related Research Unit(s)

Detail(s)

Original languageEnglish
Pages (from-to)9912−9923
Number of pages12
Journal / PublicationInorganic Chemistry
Volume62
Issue number25
Online published13 Jun 2023
Publication statusPublished - 26 Jun 2023

Abstract

Despite growing interest in the potential applications of p-block hydroperoxo complexes, the chemistry of inorganic hydroperoxides remains largely unexplored. For instance, single-crystal structures of antimony hydroperoxo complexes have not been reported to date. Herein, we present the synthesis of six triaryl and trialkylantimony dihydroperoxides [Me3Sb(OOH)2, Me3Sb(OOH)2·H2O, Ph3Sb(OOH)2·0.75(C4H8O), Ph3Sb(OOH)2·2CH3OH, pTol3Sb(OOH)2, pTol3Sb(OOH)2·2(C4H8O)], obtained by the reaction of the corresponding dibromide antimony(V) complexes with an excess of highly concentrated hydrogen peroxide in the presence of ammonia. The obtained compounds were characterized by single-crystal and powder X-ray diffraction, Fourier transform infrared and Raman spectroscopies, and thermal analysis. The crystal structures of all six compounds reveal hydrogen-bonded networks formed by hydroperoxo ligands. In addition to the previously reported double hydrogen bonding, new types of hydrogen-bonded motifs formed by hydroperoxo ligands were found, including infinite hydroperoxo chains. Solid-state density functional theory calculation of Me3Sb(OOH)2 revealed reasonably strong hydrogen bonding between OOH ligands with an energy of 35 kJ/mol. Additionally, the potential application of Ph3Sb(OOH)2·0.75(C4H8O) as a two-electron oxidant for the enantioselective epoxidation of olefins was investigated in comparison with Ph3SiOOH, Ph3PbOOH, t-BuOOH, and H2O2. © 2023 American Chemical Society.

Citation Format(s)

Organoantimony Dihydroperoxides: Synthesis, Crystal Structures, and Hydrogen Bonding Networks. / Egorov, Pavel A.; Grishanov, Dmitry A.; Medvedev, Alexander G. et al.
In: Inorganic Chemistry, Vol. 62, No. 25, 26.06.2023, p. 9912−9923.

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review