Comparing the S-T0 Nuclear Spin Conversion in the Intermediates of Homogeneous and Heterogeneous Hydrogenations with Parahydrogen

Comparing the S-T0 Nuclear Spin Conversion in the Intermediates of Homogeneous and Heterogeneous Hydrogenations with Parahydrogen Научная публикация

Журнал

The Journal of Physical Chemistry Letters
ISSN: 1948-7185

Вых. Данные

Год: 2026, Том: 17, Номер: 4, Страницы: 1173–1181 Страниц : 9 DOI: 10.1021/acs.jpclett.5c03361

Авторы

Babenko S.V. ¹ , Burueva D.B. ¹ , Kovtunova L.M. ² , Koptyug I.V. ¹

Организации

1	International Tomography Center SB RAS, 3A Institutskaya St., Novosibirsk 630090, Russia
2	Boreskov Institute of Catalysis, SB RAS, Lavrentiev Ave. 5., Novosibirsk 630090, Russia

In this work, we present an initial attempt to study the S-T0 nuclear spin conversion in the pair of p-H2-derived protons within the hydrogenation intermediates under heterogeneous conditions. The results differ significantly from those obtained under homogeneous conditions, where the S-T0 conversion demonstrated significant sensitivity to external factors, including temperature, solvent, and catalyst. The singlet character of the p-H2-derived protons transferred to the product molecule is also increased if strong continuous-wave (CW) irradiation is applied at the anticipated chemical shift of the hydrogenation intermediates during p-H2 bubbling. In contrast, under heterogeneous hydrogenation conditions, there is no or only a subtle dependence of the apparent S-T0 conversion in the hydrogenation intermediates on temperature and other external factors for all the catalysts tested. We have used the reaction of hydrogenation of 2-butyne with p-H2 to study the S-T0 conversion at the intermediates both in the gas phase and in the liquid phase. The three types of heterogeneous catalysts, monometallic (Rh/TiO2), bimetallic (Rh-In/SiO2), and immobilized complex (IrCl-P-TiO2), have demonstrated different results in terms of S-T0 conversion. At the same time, the three immobilized complexes (IrL′-L″-support) with different supports (SiO2/TiO2), as well as linkers (L″ = -P/-S) and coordination spheres (L′ = OMe or Cl), demonstrated the same results. This indicates that the S-T0 conversion depends mainly on the type of active species of the catalyst.

Babenko S.V. , Burueva D.B. , Kovtunova L.M. , Koptyug I.V.
Comparing the S-T0 Nuclear Spin Conversion in the Intermediates of Homogeneous and Heterogeneous Hydrogenations with Parahydrogen
The Journal of Physical Chemistry Letters. 2026. V.17. N4. P.1173–1181. DOI: 10.1021/acs.jpclett.5c03361 WOS

Поступила в редакцию:	27 окт. 2025 г.
Принята к публикации:	12 янв. 2026 г.
Опубликована online:	16 янв. 2026 г.
Опубликована в печати:	29 янв. 2026 г.

Web of science:

WOS:001663779000001

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