Cage-like manganesesilsesquioxanes: features of their synthesis, unique structure, and catalytic activity in oxidative amidations

Grigorii S. Astakhov; Victor N. Khrustalev; Marina S. Dronova; Evgenii I. Gutsul; Alexander A. Korlyukov; Dmitri Gelman; Yan V. Zubavichus; Daniil A. Novichkov; Alexander L. Trigub; Elena S. Shubina; Alexey N. Bilyachenko

doi:10.1039/d2qi01054b

Cage-like manganesesilsesquioxanes: features of their synthesis, unique structure, and catalytic activity in oxidative amidations

Grigorii S. Astakhov, Victor N. Khrustalev, Marina S. Dronova, Evgenii I. Gutsul, Alexander A. Korlyukov, Dmitri Gelman^*, Yan V. Zubavichus, Daniil A. Novichkov, Alexander L. Trigub, Elena S. Shubina, Alexey N. Bilyachenko^*

^*Corresponding author for this work

Institute of Chemistry

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

7 Scopus citations

Abstract

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 Mn^II to Mn^III 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 (Na^I, Mn^II, and Mn^III). 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).

Original language	American English
Pages (from-to)	4525-4537
Number of pages	13
Journal	Inorganic Chemistry Frontiers
Volume	9
Issue number	17
Early online date	14 Jul 2022
DOIs	https://doi.org/10.1039/d2qi01054b
State	E-pub ahead of print - 14 Jul 2022

Bibliographical note

Funding Information:
This work was financially supported by the Russian Science Foundation (project no. 22-13-00250). Elemental analysis data were collected using the equipment of the Center for Molecular Composition Studies of INEOS RAS with the support from the Ministry of Science and Higher Education of the Russian Federation. D. G. acknowledges the RUDN University Scientific Projects Grant System, project no. 025239-2-174, Israel Science Foundation (ISF) grant no. 370/20 and the Esther K. and M. Mark Watkins Chair for Synthetic Organic Chemistry. XANES experiment was supported by the Ministry of Education of the Russian Federation: No. 075-15-2022-1107.

Publisher Copyright:
© 2022 The Royal Society of Chemistry.

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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. (2022). Cage-like manganesesilsesquioxanes: features of their synthesis, unique structure, and catalytic activity in oxidative amidations. Inorganic Chemistry Frontiers, 9(17), 4525-4537. Advance online publication. https://doi.org/10.1039/d2qi01054b

@article{7d45f6b3387d4309beccb0ebb7b4a956,

title = "Cage-like manganesesilsesquioxanes: features of their synthesis, unique structure, and catalytic activity in oxidative amidations",

abstract = "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).",

author = "Astakhov, {Grigorii S.} and Khrustalev, {Victor N.} and Dronova, {Marina S.} and Gutsul, {Evgenii I.} and Korlyukov, {Alexander A.} and Dmitri Gelman and Zubavichus, {Yan V.} and Novichkov, {Daniil A.} and Trigub, {Alexander L.} and Shubina, {Elena S.} and Bilyachenko, {Alexey N.}",

note = "Funding Information: This work was financially supported by the Russian Science Foundation (project no. 22-13-00250). Elemental analysis data were collected using the equipment of the Center for Molecular Composition Studies of INEOS RAS with the support from the Ministry of Science and Higher Education of the Russian Federation. D. G. acknowledges the RUDN University Scientific Projects Grant System, project no. 025239-2-174, Israel Science Foundation (ISF) grant no. 370/20 and the Esther K. and M. Mark Watkins Chair for Synthetic Organic Chemistry. XANES experiment was supported by the Ministry of Education of the Russian Federation: No. 075-15-2022-1107. Publisher Copyright: {\textcopyright} 2022 The Royal Society of Chemistry.",

year = "2022",

month = jul,

day = "14",

doi = "10.1039/d2qi01054b",

language = "American English",

volume = "9",

pages = "4525--4537",

journal = "Inorganic Chemistry Frontiers",

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Astakhov, GS, Khrustalev, VN, Dronova, MS, Gutsul, EI, Korlyukov, AA, Gelman, D, Zubavichus, YV, Novichkov, DA, Trigub, AL, Shubina, ES & Bilyachenko, AN 2022, 'Cage-like manganesesilsesquioxanes: features of their synthesis, unique structure, and catalytic activity in oxidative amidations', Inorganic Chemistry Frontiers, vol. 9, no. 17, pp. 4525-4537. https://doi.org/10.1039/d2qi01054b

TY - JOUR

T1 - Cage-like manganesesilsesquioxanes

T2 - features of their synthesis, unique structure, and catalytic activity in oxidative amidations

AU - Astakhov, Grigorii S.

AU - Khrustalev, Victor N.

AU - Dronova, Marina S.

AU - Gutsul, Evgenii I.

AU - Korlyukov, Alexander A.

AU - Gelman, Dmitri

AU - Zubavichus, Yan V.

AU - Novichkov, Daniil A.

AU - Trigub, Alexander L.

AU - Shubina, Elena S.

AU - Bilyachenko, Alexey N.

N1 - Funding Information: This work was financially supported by the Russian Science Foundation (project no. 22-13-00250). Elemental analysis data were collected using the equipment of the Center for Molecular Composition Studies of INEOS RAS with the support from the Ministry of Science and Higher Education of the Russian Federation. D. G. acknowledges the RUDN University Scientific Projects Grant System, project no. 025239-2-174, Israel Science Foundation (ISF) grant no. 370/20 and the Esther K. and M. Mark Watkins Chair for Synthetic Organic Chemistry. XANES experiment was supported by the Ministry of Education of the Russian Federation: No. 075-15-2022-1107. Publisher Copyright: © 2022 The Royal Society of Chemistry.

PY - 2022/7/14

Y1 - 2022/7/14

N2 - 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).

AB - 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).

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U2 - 10.1039/d2qi01054b

DO - 10.1039/d2qi01054b

M3 - Article

AN - SCOPUS:85134852954

SN - 2052-1545

VL - 9

SP - 4525

EP - 4537

JO - Inorganic Chemistry Frontiers

JF - Inorganic Chemistry Frontiers

IS - 17

ER -

Cage-like manganesesilsesquioxanes: features of their synthesis, unique structure, and catalytic activity in oxidative amidations

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