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

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.