Cu6- and Cu8-Cage Sil- and Germsesquioxanes: Synthetic and Structural Features, Oxidative Rearrangements, and Catalytic Activity Full article
| Journal |
Inorganic Chemistry
ISSN: 0020-1669 , E-ISSN: 1520-510X |
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| Output data | Year: 2021, Volume: 60, Number: 11, Pages: 8062-8074 Pages count : 13 DOI: 10.1021/acs.inorgchem.1c00586 | ||||||||||||||
| Tags | Catalyst activity; Catalytic oxidation; Coordination reactions; Ketones; Oxidation; Single crystals; Synchrotron radiation; Volatile fatty acids | ||||||||||||||
| Authors |
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| Affiliations |
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Funding (8)
| 1 | Russian Foundation for Basic Research | 19-03-00488 (АААА-А19-119011690147-2) |
| 2 | The Ministry of Education and Science of the Russian Federation | 14.619.21.0007 (RFMEFI61917X0007)(АААА-А18-118011190114-0) |
| 3 | Ministry of Science and Higher Education of the Russian Federation | 0239-2021-0002 |
| 4 | Ministry of Science and Higher Education of the Russian Federation | 075-03-2020-223 (FSSF-2020-0017) |
| 5 | Foundation for Science and Technology | UIDB/00100/2020 |
| 6 | Foundation for Science and Technology | LISBOA-01-0145-FEDER-029697 |
| 7 | Foundation for Science and Technology | PTDC/QUI-QIN/3898/2020 |
| 8 | Foundation for Science and Technology | CEECIND/03708/2017 |
Abstract:
This study reports intriguing features in the self-assembly of cage copper(II) silsesquioxanes in the presence of air. Despite the wide variation of solvates used, a series of prismatic hexanuclear Cu6 cages (1–5) were assembled under mild conditions. In turn, syntheses at higher temperatures are accompanied by side reactions, leading to the oxidation of solvates (methanol, 1-butanol, and tetrahydrofuran). The oxidized solvent derivatives then specifically participate in the formation of copper silsesquioxane cages, allowing the isolation of several unusual Cu8-based (6 and 7) and Cu6-based (8) complexes. When 1,4-dioxane was applied as a reaction medium, deep rearrangements occurred (with a total elimination of silsesquioxane ligands), causing the formation of mononuclear copper(II) compounds bearing oxidized dioxane fragments (9 and 11) or a formate-driven 1D coordination polymer (10). Finally, a “directed” self-assembly of sil- and germsesquioxanes from copper acetate (or formate) resulted in the corresponding acetate (or formate) containing Cu6 cages (12 and 13) that were isolated in high yields. The structures of all of the products 1–13 were established by single-crystal X-ray diffraction, mainly based on the use of synchrotron radiation. Moreover, the catalytic activity of compounds 12 and 13 was evaluated toward the mild homogeneous oxidation of C5–C8 cycloalkanes with hydrogen peroxide to form a mixture of the corresponding cyclic alcohols and ketones.
Cite:
Astakhov G.S.
, Levitsky M.M.
, Zubavichus Y.V.
, Khrustalev V.N.
, Titov A.A.
, Dorovatovskii P.V.
, Smol’yakov A.F.
, Shubina E.S.
, Kirillova M.V.
, Kirillov A.M.
, Bilyachenko A.N.
Cu6- and Cu8-Cage Sil- and Germsesquioxanes: Synthetic and Structural Features, Oxidative Rearrangements, and Catalytic Activity
Inorganic Chemistry. 2021. V.60. N11. P.8062-8074. DOI: 10.1021/acs.inorgchem.1c00586 WOS Scopus РИНЦ AN PMID OpenAlex
Cu6- and Cu8-Cage Sil- and Germsesquioxanes: Synthetic and Structural Features, Oxidative Rearrangements, and Catalytic Activity
Inorganic Chemistry. 2021. V.60. N11. P.8062-8074. DOI: 10.1021/acs.inorgchem.1c00586 WOS Scopus РИНЦ AN PMID OpenAlex
Dates:
| Submitted: | Feb 26, 2021 |
| Published online: | May 12, 2021 |
| Published print: | Jun 7, 2021 |
Identifiers:
| Web of science: | WOS:000661306200048 |
| Scopus: | 2-s2.0-85106385734 |
| Elibrary: | 46840779 |
| Chemical Abstracts: | 2021:1062073 |
| PMID: | 33979518 |
| OpenAlex: | W3160061430 |