Cage-Like Manganesesilsesquioxanes: Features of Their Synthesis, Unique Structure, and Catalytic Activity in Oxidative Amidations | Sciact - CRIS-system of Boreskov Institute of Catalysis

Cage-Like Manganesesilsesquioxanes: Features of Their Synthesis, Unique Structure, and Catalytic Activity in Oxidative Amidations Full article

Journal

Inorganic Chemistry Frontiers
ISSN: 2052-1545 , E-ISSN: 2052-1553

Output data

Year: 2022, Volume: 9, Number: 17, Pages: 4525-4537 Pages count : 13 DOI: 10.1039/d2qi01054b

Tags

Catalyst activity; Chlorine compounds; Complexation; Metal ions; Metals; Single crystals

Authors

Astakhov Grigorii S. ^1,3 , Khrustalev Victor N. ^1,2 , Dronova Marina S. ³ , Gutsul Evgenii I. ³ , Korlyukov Alexander A. ^3,4 , Gelman Dmitri ⁵ , Zubavichus Yan V. ⁶ , Novichkov Daniil A. ⁷ , Trigub Alexander L. ⁸ , Shubina Elena S. ³ , Bilyachenko Alexey N. ^1,3

Affiliations

1	Peoples’ Friendship University of Russia, Miklukho-Maklay Street, 6, 117198 Moscow, Russia
2	Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect 47, Moscow 119991, Russia
3	A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Street, 28, 119991 Moscow, Russia
4	Pirogov Russian National Research Medical University, Ostrovitianov Str., 1, Moscow 117997, Russia
5	Institute of Chemistry, Edmond J. Safra Campus, The Hebrew University of Jerusalem, Jerusalem 91904, Israel
6	Boreskov Institute of Catalysis SB RAS, prosp. Akad. Lavrentieva, 5, Novosibirsk 630090, Russia
7	Department of Chemistry, Lomonosov Moscow State University, Leninskie Gory 1, Bld. 3, Moscow 119991, Russian Federation
8	National Research Center “Kurchatov Institute”, Akademika Kurchatova pl., 1, 123182 Moscow, Russia

Funding (4)

1	Israel Science Foundation	370/20
2	Russian Science Foundation	22-13-00250 (122080800011-9)
3	Peoples' Friendship University of Russia	025239-2-174
4	Ministry of Science and Higher Education of the Russian Federation	075-15-2022-1107 (122071400020-3)

An extended series of Mn-based cage-like phenylsilsesquioxanes were obtained via convenient self-assembly reactions and complexations with 1,10-phenanthroline. The structural features of these cage complexes such as (i) various nuclearities and types of silsesquioxane ligands, (ii) encapsulations of hydroxide and chloride species, and (iii) spontaneous oxidations of MnII to MnIII are established by single-crystal X-ray diffraction, including the use of synchrotron radiation. One of the synthesized compounds represents a unique feature among metallacomplexes – the presence of three metal ions with different oxidation states (NaI, MnII, and MnIII). Furthermore, the first-ever evaluation of Mn–silsesquioxanes as precatalysts in oxidative amidation (OA) reactions allowed us to develop a very effective protocol of OA of alcohols and aldehydes with low loading of Mn (5 mol% and 2.5 mol%, respectively).

Astakhov G.S. , Khrustalev V.N. , Dronova M.S. , Gutsul E.I. , Korlyukov A.A. , Gelman D. , Zubavichus Y.V. , Novichkov D.A. , Trigub A.L. , Shubina E.S. , Bilyachenko A.N.
Cage-Like Manganesesilsesquioxanes: Features of Their Synthesis, Unique Structure, and Catalytic Activity in Oxidative Amidations
Inorganic Chemistry Frontiers. 2022. V.9. N17. P.4525-4537. DOI: 10.1039/d2qi01054b WOS Scopus РИНЦ AN OpenAlex

Submitted:	May 13, 2022
Accepted:	Jul 10, 2022
Published online:	Jul 14, 2022
Published print:	Sep 7, 2022

Web of science:	WOS:000828707500001
Scopus:	2-s2.0-85134852954
Elibrary:	54728658
Chemical Abstracts:	2022:1891489
OpenAlex:	W4285412904

DB	Citing
Scopus	16
Web of science	16
OpenAlex	16
Elibrary	15