A Hafnium-Substituted Lindqvist Polyoxotungstate: Synthesis, Characterization, and Catalysis of H2O2-Based Oxidations

A Hafnium-Substituted Lindqvist Polyoxotungstate: Synthesis, Characterization, and Catalysis of H2O2-Based Oxidations Научная публикация

Журнал

Inorganic Chemistry
ISSN: 0020-1669

Вых. Данные

Год: 2026, Том: 65, Номер: 17, Страницы: 9348–9358 Страниц : 11 DOI: 10.1021/acs.inorgchem.5c05363

Авторы

Evtushok Vasilii Yu ¹ , Zalomaeva Olga V. ¹ , Maksimchuk Nataliya V. ¹ , Kozulin Fedor S. ¹ , Ivanchikova Irina D. ¹ , Yudin Vasiliy N. ² , Yanshole Vadim V. ³ , Kholdeeva Oxana A. ¹

Организации

1	Boreskov Institute of Catalysis SB RAS, Acad. Lavrentiev Ave. 5, 630090 Novosibirsk, Russia
2	Nikolaev Institute of Inorganic Chemistry SB RAS, Acad. Lavrentiev Ave. 3, 630090 Novosibirsk, Russia
3	International Tomography Center SB RAS, Institutskaya str. 3a, 630090 Novosibirsk, Russia

In this work, we first synthesized a Hf-substituted Lindqvist-type dimeric polyoxotungstate, (nBu4N)6[{HfW5O18(μ-OH)}2] ({HfW5}2), and compared its synthetic availability, structure, and catalytic performance in H2O2-based oxidations with the zirconium analogue (nBu4N)6[{ZrW5O18(μ-OH)}2] ({ZrW5}2). The {HfW5}2 dimer was characterized by single-crystal and powder X-ray diffraction analysis, elemental analysis, thermogravimetric analysis, Fourier-transform infrared spectroscopy, nuclear magnetic resonance spectroscopy (17O, 183W), and high-resolution electrospray ionization mass spectrometry, and benchmarked against {ZrW5}2. Despite the similar structures of {HfW5}2 and {ZrW5}2, the former revealed a ca. 5 times higher rate of thioanisole oxidation with aqueous H2O2 and a lower rate of unproductive H2O2 dismutation as compared to {ZrW5}2. In singlet-oxygen probe reactions (oxidation of tetramethylethylene and α-terpinene), {HfW5}2 generated products typical of 1O2 involvement but with modestly lower yields and rates than those of the Zr analogue under identical conditions. These results demonstrate that replacing Zr(IV) with more oxophilic Hf(IV) in the Lindqvist tungstate meaningfully impacts the catalytic performance in H2O2-based oxidations.

Evtushok V.Y. , Zalomaeva O.V. , Maksimchuk N.V. , Kozulin F.S. , Ivanchikova I.D. , Yudin V.N. , Yanshole V.V. , Kholdeeva O.A.
A Hafnium-Substituted Lindqvist Polyoxotungstate: Synthesis, Characterization, and Catalysis of H2O2-Based Oxidations
Inorganic Chemistry. 2026. V.65. N17. P.9348–9358. DOI: 10.1021/acs.inorgchem.5c05363 WOS Scopus OpenAlex

Поступила в редакцию:	14 нояб. 2025 г.
Принята к публикации:	8 апр. 2026 г.
Опубликована online:	18 апр. 2026 г.
Опубликована в печати:	4 мая 2026 г.

≡ Web of science:	WOS:001743677000001
≡ Scopus:	2-s2.0-105037858459
≡ OpenAlex:	W7154826041