Activation of tert‐Butyl Hydroperoxide by Zr(IV) Stabilized by Polyoxotungstate Scaffolds | Sciact - CRIS-система Института катализа

Activation of tert‐Butyl Hydroperoxide by Zr(IV) Stabilized by Polyoxotungstate Scaffolds Научная публикация

Журнал

ChemPlusChem
ISSN: 2192-6506

Вых. Данные

Год: 2024, DOI: 10.1002/cplu.202400605

Ключевые слова

alkylperoxo complexes • polyoxometalate • selective oxidation • tert-butyl hydroperoxide • zirconium

Авторы

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

Организации

1	Boreskov Institute of Catalysis, Pr. Lavrentieva 5, Novosibirsk 630090, Russia
2	International Tomography Center SB RAS, Institutskaya str. 3A, Novosibirsk 630090, Russia

Информация о финансировании (1)

Российский научный фонд

23-13-00156

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.

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

Поступила в редакцию:	16 сент. 2024 г.
Принята к публикации:	28 нояб. 2024 г.
Опубликована online:	28 нояб. 2024 г.

Web of science:	WOS:001375987700001
Scopus:	2-s2.0-85211776750
РИНЦ:	79352947
PMID (PubMed):	39606905
OpenAlex:	W4404825551

Пока нет цитирований