Nature of the Reactive Intermediates from the Titanium-Induced Activation of Hydrogen Peroxide: Studies Using 1H and 17O NMR Full article
| Journal |
Journal of Molecular Catalysis A: Chemical
ISSN: 1381-1169 |
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| Output data | Year: 1996, Volume: 106, Number: 3, Pages: 179-185 Pages count : 7 DOI: 10.1016/1381-1169(95)00278-2 | ||||
| Tags | Epoxidation, NMR spectroscopy, Peroxo complexes, Titanium | ||||
| Authors |
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| Affiliations |
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Funding (2)
| 1 | Russian Foundation for Basic Research | 93-03-4759 |
| 2 | International Association for the Promotion of Co-operation with Scientists from the New Independent States of the Former Soviet Union | 94-1515 |
Abstract:
Using 17O and 1H NMR, peroxotitanium species formed in the reaction of TiO(acac)2 and Ti(OEt)4 with H2O2 in CHCl3 were characterized. Dinuclear μ-oxo, μ-peroxo complex [Ti(acac)2]2O(O2) was prepared via reaction of TiO(acac)2 with H2O2 in CHCl3. This complex is inert towards alkenes oxidation. When Ti(OEt)4 reacts with an equimolar amount of 95% H2O2 in CHCl3 at 293 K, ca. 75% of the initial titanium complex converts to the oligomeric peroxotitanium species, containing no alkoxo ligands, ca. 20% of titanium exists in solution in the form of dinuclear μ-oxo, μ-peroxo complexes of the type [Ti(OEt)2L2]2O(O2), where L is solvent or EtOH, and 3–5% in the form of mononuclear peroxo complexes of the type Ti(O2)(OEt)2L2. Oligomeric and dinuclear peroxotitanium species were inert towards alkenes and phenol; in contrast mononuclear ones oxidize cyclohexene at 293 K predominantly into cyclohexene oxide and phenol into a 1:3 catechol/hydroquinone mixture. Peroxo complex Ti(O2)(OEt)2L2 is the first peroxotitanium complex active towards oxidation of organic substrates.
Cite:
Talsi E.P.
, Babushkin D.E.
Nature of the Reactive Intermediates from the Titanium-Induced Activation of Hydrogen Peroxide: Studies Using 1H and 17O NMR
Journal of Molecular Catalysis A: Chemical. 1996. V.106. N3. P.179-185. DOI: 10.1016/1381-1169(95)00278-2 WOS Scopus РИНЦ ANCAN OpenAlex
Nature of the Reactive Intermediates from the Titanium-Induced Activation of Hydrogen Peroxide: Studies Using 1H and 17O NMR
Journal of Molecular Catalysis A: Chemical. 1996. V.106. N3. P.179-185. DOI: 10.1016/1381-1169(95)00278-2 WOS Scopus РИНЦ ANCAN OpenAlex
Dates:
| Submitted: | Feb 21, 1995 |
| Accepted: | Oct 16, 1995 |
| Published print: | Apr 10, 1996 |
| Published online: | Oct 7, 1998 |
Identifiers:
| Web of science: | WOS:A1996UE53100001 |
| Scopus: | 2-s2.0-0013119420 |
| Elibrary: | 13241797 |
| Chemical Abstracts: | 1996:186762 |
| Chemical Abstracts (print): | 124:330635 |
| OpenAlex: | W2071634911 |