TY - JOUR
T1 - Organoantimony Dihydroperoxides
T2 - Synthesis, Crystal Structures, and Hydrogen Bonding Networks
AU - Egorov, Pavel A.
AU - Grishanov, Dmitry A.
AU - Medvedev, Alexander G.
AU - Churakov, Andrei V.
AU - Mikhaylov, Alexey A.
AU - Ottenbacher, Roman V.
AU - Bryliakov, Konstantin P.
AU - Babak, Maria V.
AU - Lev, Ovadia
AU - Prikhodchenko, Petr V.
N1 - Publisher Copyright:
© 2023 American Chemical Society.
PY - 2023/6/26
Y1 - 2023/6/26
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85163716637&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.3c00929
DO - 10.1021/acs.inorgchem.3c00929
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C2 - 37311066
AN - SCOPUS:85163716637
SN - 0020-1669
VL - 62
SP - 9912
EP - 9923
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 25
ER -