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Activation of tert‐Butyl Hydroperoxide by Zr(IV) Stabilized by Polyoxotungstate Scaffolds Full article

Journal ChemPlusChem
ISSN: 2192-6506
Output data Year: 2024, DOI: 10.1002/cplu.202400605
Tags alkylperoxo complexes • polyoxometalate • selective oxidation • tert-butyl hydroperoxide • zirconium
Authors Ivanchikova Irina D. 1 , Maksimchuk Nataliya V. 1 , Marikovskaya Sofia M. 1 , Evtushok Vasilii Yu. 1 , Antonov Artem A. 1 , Yanshole Vadim V. 2 , Kholdeeva Oxana A. 1
Affiliations
1 Boreskov Institute of Catalysis, Pr. Lavrentieva 5, Novosibirsk 630090, Russia
2 International Tomography Center SB RAS, Institutskaya str. 3A, Novosibirsk 630090, Russia

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. 2024. DOI: 10.1002/cplu.202400605 WOS Scopus РИНЦ PMID OpenAlex
Dates:
Submitted: Sep 16, 2024
Accepted: Nov 28, 2024
Published online: Nov 28, 2024
Identifiers:
Web of science: WOS:001375987700001
Scopus: 2-s2.0-85211776750
Elibrary: 79352947
PMID: 39606905
OpenAlex: W4404825551
Citing: Пока нет цитирований
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