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

Alexey N. Bilyachenko; Victor N. Khrustalev; Anna Y. Zueva; Ekaterina M. Titova; Grigorii S. Astakhov; Yan V. Zubavichus; Pavel V. Dorovatovskii; Alexander A. Korlyukov; Lidia S. Shul’pina; Elena S. Shubina; Yuriy N. Kozlov; Nikolay S. Ikonnikov; Dmitri Gelman; Georgiy B. Shul’pin

doi:10.3390/molecules27196205

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

Alexey N. Bilyachenko^*, Victor N. Khrustalev, Anna Y. Zueva, Ekaterina M. Titova, Grigorii S. Astakhov, Yan V. Zubavichus, Pavel V. Dorovatovskii, Alexander A. Korlyukov, Lidia S. Shul’pina, Elena S. Shubina, Yuriy N. Kozlov, Nikolay S. Ikonnikov, Dmitri Gelman, Georgiy B. Shul’pin^*

^*Corresponding author for this work

Institute of Chemistry

Research output: Contribution to journal › Article › peer-review

4 Scopus citations

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.

Original language	American English
Article number	6205
Journal	Molecules
Volume	27
Issue number	19
DOIs	https://doi.org/10.3390/molecules27196205
State	Published - Oct 2022

Bibliographical note

Funding Information:
This work was performed within the framework of the Program of Fundamental Research of the Russian Federation. Reg. No. 122040500068-0. Elemental and GC analyses were performed with the financial support from the Ministry of Education and Science of the Russian Federation using equipment from the Center for molecular composition studies of INEOS RAS. D.G. acknowledges RUDN University Scientific Projects Grant System, project No. 025239-2-174, the ISF (Israel Science Foundation) Grant No. 370/20 and Esther K. and M. Mark Watkins Chair for Synthetic Organic Chemistry.

Funding Information:
This research was funded by the Russian Science Foundation, grant number 22-13-00252.

Publisher Copyright:
© 2022 by the authors.

Keywords

8-hydroxyquinoline ligands
alkanes
alkyl hydroperoxide
cage-like compounds
coordination polymers
half-sandwich units
metallasilsesquioxanes
oxidative catalysis

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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. (2022). A Novel Family of Cage-like (CuLi, CuNa, CuK)-phenylsilsesquioxane Complexes with 8-Hydroxyquinoline Ligands: Synthesis, Structure, and Catalytic Activity. Molecules, 27(19), Article 6205. https://doi.org/10.3390/molecules27196205

@article{b356834581de41559edd7f7d3b0a06db,

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

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.",

keywords = "8-hydroxyquinoline ligands, alkanes, alkyl hydroperoxide, cage-like compounds, coordination polymers, half-sandwich units, metallasilsesquioxanes, oxidative catalysis",

author = "Bilyachenko, {Alexey N.} and Khrustalev, {Victor N.} and Zueva, {Anna Y.} and Titova, {Ekaterina M.} and Astakhov, {Grigorii S.} and Zubavichus, {Yan V.} and Dorovatovskii, {Pavel V.} and Korlyukov, {Alexander A.} and Shul{\textquoteright}pina, {Lidia S.} and Shubina, {Elena S.} and Kozlov, {Yuriy N.} and Ikonnikov, {Nikolay S.} and Dmitri Gelman and Shul{\textquoteright}pin, {Georgiy B.}",

note = "Funding Information: This work was performed within the framework of the Program of Fundamental Research of the Russian Federation. Reg. No. 122040500068-0. Elemental and GC analyses were performed with the financial support from the Ministry of Education and Science of the Russian Federation using equipment from the Center for molecular composition studies of INEOS RAS. D.G. acknowledges RUDN University Scientific Projects Grant System, project No. 025239-2-174, the ISF (Israel Science Foundation) Grant No. 370/20 and Esther K. and M. Mark Watkins Chair for Synthetic Organic Chemistry. Funding Information: This research was funded by the Russian Science Foundation, grant number 22-13-00252. Publisher Copyright: {\textcopyright} 2022 by the authors.",

year = "2022",

month = oct,

doi = "10.3390/molecules27196205",

language = "American English",

volume = "27",

journal = "Molecules",

issn = "1420-3049",

publisher = "MDPI Multidisciplinary Digital Publishing Institute",

number = "19",

}

Bilyachenko, AN, Khrustalev, VN, Zueva, AY, Titova, EM, Astakhov, GS, Zubavichus, YV, Dorovatovskii, PV, Korlyukov, AA, Shul’pina, LS, Shubina, ES, Kozlov, YN, Ikonnikov, NS, Gelman, D & Shul’pin, GB 2022, 'A Novel Family of Cage-like (CuLi, CuNa, CuK)-phenylsilsesquioxane Complexes with 8-Hydroxyquinoline Ligands: Synthesis, Structure, and Catalytic Activity', Molecules, vol. 27, no. 19, 6205. https://doi.org/10.3390/molecules27196205

TY - JOUR

T1 - A Novel Family of Cage-like (CuLi, CuNa, CuK)-phenylsilsesquioxane Complexes with 8-Hydroxyquinoline Ligands

T2 - Synthesis, Structure, and Catalytic Activity

AU - Bilyachenko, Alexey N.

AU - Khrustalev, Victor N.

AU - Zueva, Anna Y.

AU - Titova, Ekaterina M.

AU - Astakhov, Grigorii S.

AU - Zubavichus, Yan V.

AU - Dorovatovskii, Pavel V.

AU - Korlyukov, Alexander A.

AU - Shul’pina, Lidia S.

AU - Shubina, Elena S.

AU - Kozlov, Yuriy N.

AU - Ikonnikov, Nikolay S.

AU - Gelman, Dmitri

AU - Shul’pin, Georgiy B.

N1 - Funding Information: This work was performed within the framework of the Program of Fundamental Research of the Russian Federation. Reg. No. 122040500068-0. Elemental and GC analyses were performed with the financial support from the Ministry of Education and Science of the Russian Federation using equipment from the Center for molecular composition studies of INEOS RAS. D.G. acknowledges RUDN University Scientific Projects Grant System, project No. 025239-2-174, the ISF (Israel Science Foundation) Grant No. 370/20 and Esther K. and M. Mark Watkins Chair for Synthetic Organic Chemistry. Funding Information: This research was funded by the Russian Science Foundation, grant number 22-13-00252. Publisher Copyright: © 2022 by the authors.

PY - 2022/10

Y1 - 2022/10

N2 - 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.

AB - 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.

KW - 8-hydroxyquinoline ligands

KW - alkanes

KW - alkyl hydroperoxide

KW - cage-like compounds

KW - coordination polymers

KW - half-sandwich units

KW - metallasilsesquioxanes

KW - oxidative catalysis

UR - http://www.scopus.com/inward/record.url?scp=85139922984&partnerID=8YFLogxK

U2 - 10.3390/molecules27196205

DO - 10.3390/molecules27196205

M3 - Article

C2 - 36234735

AN - SCOPUS:85139922984

SN - 1420-3049

VL - 27

JO - Molecules

JF - Molecules

IS - 19

M1 - 6205

ER -

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

Abstract

Bibliographical note

Keywords

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