Role of Alkylperoxo Complexes of Cobalt (III) in Catalytic Oxidation of Cyclohexane by Cumene Hydroperoxide in the Presence of bis (acetylacetonato) Cobalt (II) Full article
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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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| Output data | Year: 1993, Volume: 81, Number: 2, Pages: 215-233 Pages count : 19 DOI: 10.1016/0304-5102(93)80008-I | ||
| Tags | 59Co NMR spectroscopy, alkylperoxo complexes, cobalt, cumene hydroperoxide, cyclohexane, oxidation mechanisms | ||
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Abstract:
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..
Cite:
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 ANCAN 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 ANCAN OpenAlex
Dates:
| Submitted: | Dec 14, 1990 |
| Accepted: | Jan 14, 1993 |
| Published print: | May 10, 1993 |
| Published online: | Oct 2, 2001 |
Identifiers:
| Web of science: | WOS:A1993LD61900008 |
| Scopus: | 2-s2.0-0027590301 |
| Elibrary: | 26563294 |
| Chemical Abstracts: | 1993:602850 |
| Chemical Abstracts (print): | 119:202850 |
| OpenAlex: | W1987426034 |