Activation of tert‐Butyl Hydroperoxide by Zr(IV) Stabilized by Polyoxotungstate Scaffolds Full article
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ChemPlusChem
ISSN: 2192-6506 |
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| Output data | Year: 2025, Volume: 90, Number: 3, Article number : e202400605, Pages count : 9 DOI: 10.1002/cplu.202400605 | ||||
| Tags | alkylperoxo complexes • polyoxometalate • selective oxidation • tert-butyl hydroperoxide • zirconium | ||||
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Funding (1)
| 1 | Russian Science Foundation | 23-13-00156 |
Abstract:
Zr-monosubstituted polyoxometalates (Zr-POMs) of the Keggin (Bu4N)8[{PW11O39Zr(μ-OH)}2] (Zr-K), Lindqvist (Bu4N)6[{W5O18Zr(μ-OH)}2] (Zr-L), and Wells-Dawson (Bu4N)11H3[{P2W17O61Zr(μ-OH)}2] (Zr-WD) structures are capable of heterolytic activation of the environmentally benign oxidant tert-butyl hydroperoxide (TBHP) and catalyze epoxidation of alkenes and oxidation of alcohols to carbonyl compounds. Catalytic activity of corresponding Ti-POMs is much lower. Among Zr-POMs, Zr-K revealed higher epoxide yields. All Zr-POMs do not catalyze unproductive TBHP degradation, and epoxide yields with both aqueous and anhydrous TBHP are generally higher than with aqueous H2O2. Regioselectivity of the Zr-K-catalyzed limonene epoxidation with TBHP is different from that with H2O2: the more substituted and nucleophilic double bond is preferably epoxidized, pointing to an electrophilic oxygen transfer mechanism. The oxidation rates are first order in catalyst (Zr-K) and substrate (cyclooctene or cyclohexanol) and show a saturation behavior with increasing concentration of TBHP. Studies by HR-ESI-MS, ATR-FT-IR, and 31P NMR spectroscopic techniques implicated the formation of zirconium alkylperoxo species upon interaction of Zr-POMs with TBHP. HR-ESI-MS revealed the existence of monomeric and dimeric alkylperoxo complexes, [{PW11O39Zr}((CH3)3COO)]4- and [{PW11O39Zr((CH3)3COO)}2]8-, with predomination of the former, which is most likely the active species responsible for the selective oxidations.
Cite:
Ivanchikova I.D.
, Maksimchuk N.V.
, Marikovskaya S.M.
, Evtushok V.Y.
, Antonov A.A.
, Yanshole V.V.
, Kholdeeva O.A.
Activation of tert‐Butyl Hydroperoxide by Zr(IV) Stabilized by Polyoxotungstate Scaffolds
ChemPlusChem. 2025. V.90. N3. e202400605 :1-9. DOI: 10.1002/cplu.202400605 WOS Scopus РИНЦ PMID OpenAlex
Activation of tert‐Butyl Hydroperoxide by Zr(IV) Stabilized by Polyoxotungstate Scaffolds
ChemPlusChem. 2025. V.90. N3. e202400605 :1-9. DOI: 10.1002/cplu.202400605 WOS Scopus РИНЦ PMID OpenAlex
Dates:
| Submitted: | Sep 16, 2024 |
| Accepted: | Nov 28, 2024 |
| Published online: | Dec 13, 2024 |
| Published print: | Mar 17, 2025 |
Identifiers:
| Web of science: | WOS:001375987700001 |
| Scopus: | 2-s2.0-85211776750 |
| Elibrary: | 79352947 |
| PMID: | 39606905 |
| OpenAlex: | W4404825551 |
Citing:
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