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

• Published in: Inorganic chemistry Vol. 62; no. 25; pp. 9912 - 9923
• Main Authors: Egorov, Pavel A., Grishanov, Dmitry A., Medvedev, Alexander G., Churakov, Andrei V., Mikhaylov, Alexey A., Ottenbacher, Roman V., Bryliakov, Konstantin P., Babak, Maria V., Lev, Ovadia, Prikhodchenko, Petr V.
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 26-06-2023
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/acs.inorgchem.3c00929

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.