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

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

Research output: Contribution to journalArticlepeer-review

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 [Me 3Sb(OOH) 2, Me 3Sb(OOH) 2·H 2O, Ph 3Sb(OOH) 2·0.75(C 4H 8O), Ph 3Sb(OOH) 2·2CH 3OH, pTol 3Sb(OOH) 2, pTol 3Sb(OOH) 2·2(C 4H 8O)], 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 Me 3Sb(OOH) 2 revealed reasonably strong hydrogen bonding between OOH ligands with an energy of 35 kJ/mol. Additionally, the potential application of Ph 3Sb(OOH) 2·0.75(C 4H 8O) as a two-electron oxidant for the enantioselective epoxidation of olefins was investigated in comparison with Ph 3SiOOH, Ph 3PbOOH, t-BuOOH, and H 2O 2.

Original languageAmerican English
Pages (from-to)9912-9923
Number of pages12
JournalInorganic Chemistry
Volume62
Issue number25
DOIs
StatePublished - 26 Jun 2023

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

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