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

Research output: Contribution to journalArticlepeer-review

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)

Original languageAmerican English
Pages (from-to)9912-9923
Number of pages12
JournalInorganic Chemistry
Volume62
Issue number25
DOIs
StatePublished - 26 Jun 2023

Bibliographical note

Funding Information:
This study was supported by the Russian Science Foundation (Grant 22-13-00426, https://rscf.ru/en/project/22-13-00426/ ; synthesis and characterization). R.V.O. acknowledges financial support from the Ministry of Science and Higher Education (Project AAAA-A21-121011390008-4) within the governmental order for Boreskov Institute of Catalysis (catalytic experiments). M.V.B. acknowledges support from the City University of Hong Kong (Project 9610518). The X-ray diffraction study was performed using the equipment of the JRC PMR IGIC RAS within the State Assignment of the Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences. The authors thank Prof. M. V. Vener for computation facilities and Dr. E. S. Belyaev and CKP FMI IPCE RAS for NMR studies.

Funding Information:
This study was supported by the Russian Science Foundation (Grant 22-13-00426, https://rscf.ru/en/project/22-13-00426/; synthesis and characterization). R.V.O. acknowledges financial support from the Ministry of Science and Higher Education (Project AAAA-A21-121011390008-4) within the governmental order for Boreskov Institute of Catalysis (catalytic experiments). M.V.B. acknowledges support from the City University of Hong Kong (Project 9610518). The X-ray diffraction study was performed using the equipment of the JRC PMR IGIC RAS within the State Assignment of the Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences. The authors thank Prof. M. V. Vener for computation facilities and Dr. E. S. Belyaev and CKP FMI IPCE RAS for NMR studies.

Publisher Copyright:
© 2023 American Chemical Society.

Fingerprint

Dive into the research topics of 'Organoantimony Dihydroperoxides: Synthesis, Crystal Structures, and Hydrogen Bonding Networks'. Together they form a unique fingerprint.

Cite this