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A Novel Family of Cage-like (CuLi, CuNa, CuK)-phenylsilsesquioxane Complexes with 8-Hydroxyquinoline Ligands: Synthesis, Structure, and Catalytic Activity Full article

Journal Molecules
ISSN: 1420-3049
Output data Year: 2022, Volume: 27, Number: 19, Article number : 6205, Pages count : 22 DOI: 10.3390/molecules27196205
Tags metallasilsesquioxanes; cage-like compounds; 8-hydroxyquinoline ligands; coordination polymers; half-sandwich units; oxidative catalysis; alkanes; alkyl hydroperoxide
Authors Bilyachenko Alexey N. 1,2 , Khrustalev Victor N. 2,3 , Zueva Anna Y. 1,2 , Titova Ekaterina M. 1 , Astakhov Grigorii S. 1,2 , Zubavichus Yan V. 4 , Dorovatovskii Pavel V. 5 , Korlyukov Alexander A. 1,6 , Shul’pina Lidia S. 1 , Shubina Elena S. 1 , Kozlov Yuriy N. 7,8 , Ikonnikov Nikolay S. 1 , Gelman Dmitri 9 , Shul’pin Georgiy B. 7,8
Affiliations
1 A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str. 28, 119991 Moscow, Russia
2 Peoples’ Friendship University of Russia (RUDN University), Miklukho-Maklay Str. 6, 117198 Moscow, Russia
3 Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences (RAS), Leninsky Prospect 47, 119991 Moscow, Russia
4 Synchrotron Radiation Facility SKIF, Boreskov Institute of Catalysis SB RAS, Nikolskii Prosp. 1, 630559 Koltsovo, Russia
5 National Research Center “Kurchatov Institute”, Akademika Kurchatova pl. 1, 123182 Moscow, Russia
6 Pirogov Russian National Research Medical University, Ostrovitianov Str. 1, 117997 Moscow, Russia
7 Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, Ulitsa Kosygina 4, 119991 Moscow, Russia
8 Chair of Chemistry and Physics, Plekhanov Russian University of Economics, Stremyannyi Pereulok, Dom 36, 117997 Moscow, Russia
9 Institute of Chemistry, Edmond J. Safra Campus, The Hebrew University of Jerusalem, Jerusalem 91904, Israel

Abstract: The first examples of metallasilsesquioxane complexes, including ligands of the 8-hydroxyquinoline family 1–9, were synthesized, and their structures were established by single crystal X-ray diffraction using synchrotron radiation. Compounds 1–9 tend to form a type of sandwich-like cage of Cu4M2 nuclearity (M = Li, Na, K). Each complex includes two cisoid pentameric silsesquioxane ligands and two 8-hydroxyquinoline ligands. The latter coordinates the copper ions and corresponding alkaline metal ions (via the deprotonated oxygen site). A characteristic (size) of the alkaline metal ion and a variation of characteristics of nitrogen ligands (8-hydroxyquinoline vs. 5-chloro-8-hydroxyquinoline vs. 5,7-dibromo-8-hydroxyquinoline vs. 5,7-diiodo-8-hydroxyquinoline) are highly influential for the formation of the supramolecular structure of the complexes 3a, 5, and 7–9. The Cu6Na2-based compound 2 exhibits high catalytic activity towards the oxidation of (i) hydrocarbons by H2O2 activated with HNO3, and (ii) alcohols by tert-butyl hydroperoxide. Studies of kinetics and their selectivity has led us to conclude that it is the hydroxyl radicals that play a crucial role in this process.
Cite: Bilyachenko A.N. , Khrustalev V.N. , Zueva A.Y. , Titova E.M. , Astakhov G.S. , Zubavichus Y.V. , Dorovatovskii P.V. , Korlyukov A.A. , Shul’pina L.S. , Shubina E.S. , Kozlov Y.N. , Ikonnikov N.S. , Gelman D. , Shul’pin G.B.
A Novel Family of Cage-like (CuLi, CuNa, CuK)-phenylsilsesquioxane Complexes with 8-Hydroxyquinoline Ligands: Synthesis, Structure, and Catalytic Activity
Molecules. 2022. V.27. N19. 6205 :1-22. DOI: 10.3390/molecules27196205 WOS Scopus AN PMID OpenAlex publication_identifier_short.sciact_skif_identifier_type
Dates:
Submitted: Aug 29, 2022
Accepted: Sep 13, 2022
Published online: Sep 21, 2022
Published print: Oct 1, 2022
Identifiers:
Web of science: WOS:000866981800001
Scopus: 2-s2.0-85139922984
Chemical Abstracts: 2022:2676212
PMID: 36234735
OpenAlex: W4296641739
publication_identifier.sciact_skif_identifier_type: 562
Citing:
DB Citing
OpenAlex 11
Scopus 13
Web of science 12
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