Cu6- and Cu8-Cage Sil- and Germsesquioxanes: Synthetic and Structural Features, Oxidative Rearrangements, and Catalytic Activity Научная публикация
| Журнал |
Inorganic Chemistry
ISSN: 0020-1669 , E-ISSN: 1520-510X |
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| Вых. Данные | Год: 2021, Том: 60, Номер: 11, Страницы: 8062-8074 Страниц : 13 DOI: 10.1021/acs.inorgchem.1c00586 | ||||||||||||||
| Ключевые слова | Catalyst activity; Catalytic oxidation; Coordination reactions; Ketones; Oxidation; Single crystals; Synchrotron radiation; Volatile fatty acids | ||||||||||||||
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| Организации |
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Информация о финансировании (8)
| 1 | Российский фонд фундаментальных исследований | 19-03-00488 (АААА-А19-119011690147-2) |
| 2 | Министерство образования и науки Российской Федерации | 14.619.21.0007 (RFMEFI61917X0007)(АААА-А18-118011190114-0) |
| 3 | Министерство науки и высшего образования Российской Федерации (с 15 мая 2018) | 0239-2021-0002 |
| 4 | Министерство науки и высшего образования Российской Федерации (с 15 мая 2018) | 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 |
Реферат:
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.
Библиографическая ссылка:
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 CAPlus 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 CAPlus PMID OpenAlex
Даты:
| Поступила в редакцию: | 26 февр. 2021 г. |
| Опубликована online: | 12 мая 2021 г. |
| Опубликована в печати: | 7 июн. 2021 г. |
Идентификаторы БД:
| Web of science: | WOS:000661306200048 |
| Scopus: | 2-s2.0-85106385734 |
| РИНЦ: | 46840779 |
| Chemical Abstracts: | 2021:1062073 |
| PMID (PubMed): | 33979518 |
| OpenAlex: | W3160061430 |