Cagelike Rb2-, K2-, and Na2-Tetracopper(II) Silsesquioxanes with Quaternary Ammonium Cations: Synthesis, Structures, and Catalytic Activity | Sciact - CRIS-system of Boreskov Institute of Catalysis

Cagelike Rb2-, K2-, and Na2-Tetracopper(II) Silsesquioxanes with Quaternary Ammonium Cations: Synthesis, Structures, and Catalytic Activity Full article

Journal

Organometallics
ISSN: 0276-7333 , E-ISSN: 1520-6041

Output data

Year: 2023, Volume: 42, Number: 18, Pages: 2577–2589 Pages count : 13 DOI: 10.1021/acs.organomet.2c00649

Authors

Bilyachenko Alexey N. ^1,2 , Khrustalev Victor N. ^2,3 , Astakhov Grigorii S. ^1,2 , Zueva Anna Y. ^1,2 , Arteev Ivan S. ^1,4 , Zubavichus Yan V. ⁵ , Korlyukov Alexander A. ^1,6 , Dorovatovskii Pavel V. ⁷ , Shul’pina Lidia S. ¹ , Ikonnikov Nikolay S. ¹ , Kirillova Marina V. ⁸ , Shubina Elena S. ¹ , Kozlov Yuriy N. ^9,10 , Kirillov Alexander M. ⁸ , Shul'pin Georgiy B. ^9,10

Affiliations

1	A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Street 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, Leninsky Prospect 47, 119991 Moscow, Russia
4	Higher Chemical College, Mendeleev University of Chemical Technology of Russia, Miusskaya Sq. 9, 125047 Moscow, Russia
5	Synchrotron Radiation Facility SKIF, Boreskov Institute of Catalysis SB RAS, Nikolskii Prospect 1, 630559 Koltsovo, Russia
6	Pirogov Russian National Research Medical University, Ostrovitianov Str. 1, 117997 Moscow, Russia
7	National Research Center “Kurchatov Institute”, Akademika Kurchatova Pl. 1, 123182 Moscow, Russia
8	Centro de Química Estrutural, Institute of Molecular Sciences, Departamento de Engenharia Química, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon, Portugal
9	N.N. Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, Ulitsa Kosygina 4, 119991 Moscow, Russia
10	Plekhanov Russian University of Economics, Stremyannyi Pereulok, Dom 36, 117997 Moscow, Russia

Ten copper-based cage silsesquioxanes were prepared via convenient self-assembly synthesis employing halides of different quaternary ammonium cations, namely, Me4NBr, Et4NBr, PhMe3NCl, BzMe3NCl, and BzEt3NCl. This approach led to cages of similar Cu4M2 nuclearity (M = Rb, K, or Na). Sandwich-like structures of all compounds were established by single-crystal X-ray diffraction studies using synchrotron radiation. In all products, anionic cages are based on two cyclic silsesquioxane [Ph6Si6O12] ligands, coordinating to a central hexagonal CuII4M2 motif with a 2M6-1 topology. The complexes include two charge balancers, namely, quaternary N-cations located at the external (crown ether-like) positions to cage fragments. Selected compounds were tested as homogeneous multicopper(II) catalysts in a series of model reactions, such as the mild oxidation and carboxylation of alkanes, including inert gaseous C2–C4 saturated hydrocarbons. This study extends the types of synthetic approaches and family of ionic metallasilsesquioxanes with promising structural features and catalytic properties.

Bilyachenko A.N. , Khrustalev V.N. , Astakhov G.S. , Zueva A.Y. , Arteev I.S. , Zubavichus Y.V. , Korlyukov A.A. , Dorovatovskii P.V. , Shul’pina L.S. , Ikonnikov N.S. , Kirillova M.V. , Shubina E.S. , Kozlov Y.N. , Kirillov A.M. , Shul'pin G.B.
Cagelike Rb2-, K2-, and Na2-Tetracopper(II) Silsesquioxanes with Quaternary Ammonium Cations: Synthesis, Structures, and Catalytic Activity
Organometallics. 2023. V.42. N18. P.2577–2589. DOI: 10.1021/acs.organomet.2c00649 WOS Scopus РИНЦ ANCAN OpenAlex publication_identifier_short.sciact_skif_identifier_type

Submitted:	Dec 26, 2022
Published online:	Mar 23, 2023
Published print:	Sep 25, 2023

Web of science:	WOS:000961993300001
Scopus:	2-s2.0-85151354354
Elibrary:	62970901
Chemical Abstracts:	2023:587171
Chemical Abstracts (print):	184:102526
OpenAlex:	W4360609269
publication_identifier.sciact_skif_identifier_type:	575

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