Organoantimony Dihydroperoxides: Synthesis, Crystal Structures, and Hydrogen Bonding Networks | Sciact - CRIS-system of Boreskov Institute of Catalysis

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

Journal

Inorganic Chemistry
ISSN: 0020-1669 , E-ISSN: 1520-510X

Output data

Year: 2023, Volume: 62, Number: 25, Pages: 9912–9923 Pages count : 12 DOI: 10.1021/acs.inorgchem.3c00929

Tags

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

Authors

Egorov Pavel A. ³ , Grishanov Dmitry A. ⁴ , Medvedev Alexander G. ³ , Churakov Andrei V. ³ , Mikhaylov Alexey A. ³ , Ottenbacher Roman V. ⁵ , Bryliakov Konstantin P. ¹ , Babak Maria V. ² , Lev Ovadia ⁴ , Prikhodchenko Petr V. ³

Affiliations

1	Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninskii pr. 47, Moscow 119991, Russian Federation
2	Drug Discovery Lab, Department of Chemistry, City University of Hong Kong, Kowloon, Hong Kong SAR 999077, China
3	Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii pr. 31, Moscow 119991, Russian Federation
4	Casali Center of Applied Chemistry, Hebrew University of Jerusalem, Jerusalem 9190401, Israel
5	Boreskov Institute of Catalysis, Pr. Lavrentieva 5, Novosibirsk 630090, Russian Federation

Funding (3)

1	Ministry of Science and Higher Education of the Russian Federation	0239-2021-0009
2	City University of Hong Kong	9610518
3	Russian Science Foundation	22-13-00426 (122080300030-5)

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.

Egorov P.A. , Grishanov D.A. , Medvedev A.G. , Churakov A.V. , Mikhaylov A.A. , Ottenbacher R.V. , Bryliakov K.P. , Babak M.V. , Lev O. , Prikhodchenko P.V.
Organoantimony Dihydroperoxides: Synthesis, Crystal Structures, and Hydrogen Bonding Networks
Inorganic Chemistry. 2023. V.62. N25. P.9912–9923. DOI: 10.1021/acs.inorgchem.3c00929 WOS Scopus РИНЦ AN PMID OpenAlex

Submitted:	Mar 21, 2023
Published online:	Jun 13, 2023
Published print:	Jun 26, 2023

Web of science:	WOS:001008553200001
Scopus:	2-s2.0-85163716637
Elibrary:	54146911
Chemical Abstracts:	2023:1198655
PMID:	37311066
OpenAlex:	W4380449922

DB	Citing
Web of science	5
Elibrary	6
OpenAlex	5
Scopus	6