Role of Alkylperoxo Complexes of Cobalt (III) in Catalytic Oxidation of Cyclohexane by Cumene Hydroperoxide in the Presence of bis (acetylacetonato) Cobalt (II) Научная публикация
| Журнал |
Journal of Molecular Catalysis (Continued after 1994 as Journal of Molecular Catalysis A: Chemical and Journal of Molecular Catalysis B: Enzymatic)
ISSN: 0304-5102 |
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| Вых. Данные | Год: 1993, Том: 81, Номер: 2, Страницы: 215-233 Страниц : 19 DOI: 10.1016/0304-5102(93)80008-I | ||
| Ключевые слова | 59Co NMR spectroscopy, alkylperoxo complexes, cobalt, cumene hydroperoxide, cyclohexane, oxidation mechanisms | ||
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| Организации |
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Реферат:
Alkylperoxo complexes of the Co(acac)2(OOR)B family (acac is acetylacetonato ligand; R = PhMe2C; B = Py, Py-d5 or 3-Br-Py) were isolated and their role in the oxidation of cyclohexane with ROOH was studied.
From 2H and 59Co NMR data obtained in benzene solutions containing Co(acac)2 + ROOH + B, cobalt exists at 20°C mainly as the Co(acac)2 (OOR)B species. In benzene solutions of Co(acac)2+ROOH that containing no B, cobalt exists mainly as three complexes of the Cox (acac)y (OH)z family.
Similar yields were found for various products of cyclohexane oxidation in benzene: cyclohexane = 1:1 solutions of Co (acac)2 + ROOH + B, where alkylperoxo complexes of CoIII prevail, and of Co (acac)2 + ROOH, where alkylperoxo complexes were not detected. This suggests that the key intermediates of cyclohexane oxidation with the Co(acac)2 + ROOH and Co(acac)2 + ROOH + B are the same. Mostprobably, they are the free radicals RO; and RO'. The role of the cobalt catalyst consists in the generation of these radicals. The formation of alkylperoxo complexes in the presence of B inhibits rather than promotes the oxidation, due to the capture of active radicals RO2..
Библиографическая ссылка:
Talsi E.P.
, Chinakov V.D.
, Babenko V.P.
, Sidelnikov V.N.
, Zamaraev K.I.
Role of Alkylperoxo Complexes of Cobalt (III) in Catalytic Oxidation of Cyclohexane by Cumene Hydroperoxide in the Presence of bis (acetylacetonato) Cobalt (II)
Journal of Molecular Catalysis (Continued after 1994 as Journal of Molecular Catalysis A: Chemical and Journal of Molecular Catalysis B: Enzymatic). 1993. V.81. N2. P.215-233. DOI: 10.1016/0304-5102(93)80008-I WOS Scopus РИНЦ CAPlusCA OpenAlex
Role of Alkylperoxo Complexes of Cobalt (III) in Catalytic Oxidation of Cyclohexane by Cumene Hydroperoxide in the Presence of bis (acetylacetonato) Cobalt (II)
Journal of Molecular Catalysis (Continued after 1994 as Journal of Molecular Catalysis A: Chemical and Journal of Molecular Catalysis B: Enzymatic). 1993. V.81. N2. P.215-233. DOI: 10.1016/0304-5102(93)80008-I WOS Scopus РИНЦ CAPlusCA OpenAlex
Даты:
| Поступила в редакцию: | 14 дек. 1990 г. |
| Принята к публикации: | 14 янв. 1993 г. |
| Опубликована в печати: | 10 мая 1993 г. |
| Опубликована online: | 2 окт. 2001 г. |
Идентификаторы БД:
| Web of science: | WOS:A1993LD61900008 |
| Scopus: | 2-s2.0-0027590301 |
| РИНЦ: | 26563294 |
| Chemical Abstracts: | 1993:602850 |
| Chemical Abstracts (print): | 119:202850 |
| OpenAlex: | W1987426034 |