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

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

来源：Inorganic Chemistry, 2023.

DOI：10.1021/acs.inorgchem.3c00929

• ELECTRON-DENSITY PROPERTIES
• GROUP-III METALS
• COMPOUND-I
• PEROXIDE COORDINATION
• MOLECULAR-STRUCTURE
• REVERSIBLE BINDING
• DFT COMPUTATIONS
• H2O2
• ACTIVATION
• IRON

Despite growing interest in the potential applicationsof p-blockhydroperoxo complexes, the chemistry of inorganic hydroperoxides remainslargely unexplored. For instance, single-crystal structures of antimonyhydroperoxo complexes have not been reported to date. Herein, we presentthe synthesis of six triaryl and trialkylantimony dihydroperoxides[Me3Sb(OOH)(2), Me3Sb(OOH)(2)center dot H2O, Ph3Sb(OOH)(2)center dot 0.75(C4H8O), Ph3Sb(OOH)(2)center dot 2CH(3)OH, pTol(3)Sb(OOH)(2), pTol(3)Sb(OOH)(2)center dot 2(C4H8O)], obtained by the reaction of the corresponding dibromideantimony(V) complexes with an excess of highly concentrated hydrogenperoxide in the presence of ammonia. The obtained compounds were characterizedby single-crystal and powder X-ray diffraction, Fourier transforminfrared and Raman spectroscopies, and thermal analysis. The crystalstructures of all six compounds reveal hydrogen-bonded networks formedby hydroperoxo ligands. In addition to the previously reported doublehydrogen bonding, new types of hydrogen-bonded motifs formed by hydroperoxoligands were found, including infinite hydroperoxo chains. Solid-statedensity functional theory calculation of Me3Sb(OOH)(2) revealed reasonably strong hydrogen bonding between OOH ligandswith an energy of 35 kJ/mol. Additionally, the potential applicationof Ph3Sb(OOH)(2)center dot 0.75(C4H8O) as a two-electron oxidant for the enantioselective epoxidationof olefins was investigated in comparison with Ph3SiOOH,Ph3PbOOH, t-BuOOH, and H2O2. @@@ This study reports the synthesis andcharacterization ofsix triaryl and trialkylantimony dihydroperoxides. New types of hydrogen-bondedmotifs formed by hydroperoxo ligands were discovered, including infinitehydroperoxo chains. The potential of triphenylantimony dihydroperoxideas a two-electron oxidant in an enantioselective epoxidation reactionwas investigated.