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

doi:10.1021/acs.inorgchem.3c00929

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^*

^*Corresponding author for this work

Department of Chemistry

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

10 Citations (Scopus)

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 [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.

Original language	English
Pages (from-to)	9912−9923
Number of pages	12
Journal	Inorganic Chemistry
Volume	62
Issue number	25
Online published	13 Jun 2023
DOIs	https://doi.org/10.1021/acs.inorgchem.3c00929
Publication status	Published - 26 Jun 2023

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@article{9a18b6b0a3a24fa5b8d99eb065c52c17,

title = "Organoantimony Dihydroperoxides: Synthesis, Crystal Structures, and Hydrogen Bonding Networks",

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 [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. {\textcopyright} 2023 American Chemical Society.",

author = "Egorov, \{Pavel A.\} and Grishanov, \{Dmitry A.\} and Medvedev, \{Alexander G.\} and Churakov, \{Andrei V.\} and Mikhaylov, \{Alexey A.\} and Ottenbacher, \{Roman V.\} and Bryliakov, \{Konstantin P.\} and Babak, \{Maria V.\} and Ovadia Lev and Prikhodchenko, \{Petr V.\}",

year = "2023",

month = jun,

day = "26",

doi = "10.1021/acs.inorgchem.3c00929",

language = "English",

volume = "62",

pages = "9912−9923",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "25",

}

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.

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 [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.

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 [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.

U2 - 10.1021/acs.inorgchem.3c00929

DO - 10.1021/acs.inorgchem.3c00929

M3 - RGC 21 - Publication in refereed journal

SN - 0020-1669

VL - 62

SP - 9912−9923

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 25

ER -

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

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