Chiral Organic Salt Supported Pd Nanoparticles as Selective Heterogeneous Catalysts of Hydrogenation Reactions

Chiral Organic Salt Supported Pd Nanoparticles as Selective Heterogeneous Catalysts of Hydrogenation Reactions Научная публикация

Журнал

ChemistrySelect
ISSN: 2365-6549

Вых. Данные

Год: 2024, Том: 9, Номер: 41, Номер статьи : e202402788, Страниц : DOI: 10.1002/slct.202402788

Авторы

Kuznetsova Svetlana A. ¹ , Yunusov Safar M. ¹ , North Michael ² , Zhereb Vladimir P. ³ , Khakina Ekaterina A. ¹ , Naumkin Alexander ¹ , Lobanov Nikolai N. ⁴ , Khrustalev Victor N. ^4,5 , Chusov Denis ¹ , Kalyuzhnaya Elena S. ¹ , Ilyin Mikhail M. ¹ , Morozov Viacheslav V. ^1,6 , Kashin Alexey S. ⁵ , Ezernitskaya Mariam G. ¹ , Belokon Yuri N. ¹

Организации

1	A.N. Nesmeyanov Institute of Organoelement Compounds Russian Academy of Sciences Vavilov Street 28 119334 Moscow Russian Federation
2	Green Chemistry Centre of Excellence Department of Chemistry University of York Heslington, York YO10 5DD UK
3	Siberian Federal University School of Non-Ferrous Metals and Material Science Krasnoyarskiy Rabochiy Pr. 95 660025 Krasnoyarsk Russian Federation
4	Peoples' Friendship University of Russia (RUDN University) Miklukho-Maklaya Street 6 Moscow 117198 Russian Federation
5	Zelinsky Institute of Organic Chemistry Leniskyi Prosp. 47 Moscow Russian Federation
6	D. Mendeleev University of Chemical Technology of Russia Miusskaya Square 9 125047 Moscow Russian Federation

In this study, we report the synthesis of a new type of chiral crystalline organic porous salt CF2 derived from the ionic reaction between tetrakis(4-sulfophenyl)methane (TSPM) and the tetra-(S)-prolylamide of tetrakis(4-aminophenyl)methane, (S)-TPPM, and its ability to stabilize 2 nm palladium nanoparticles to give a novel, nonpyrophoric, chiral, catalytic material Pd@CF2. The preparation of the catalyst was very simple and conducted in water. The heterogeneous catalytic performance of Pd@CF2 was tested in hydrogen reductions of olefins and substituted nitroaromatic compounds using Pd/C as a comparison to determine the specific features of the novel catalyst. Although both types of catalysts exhibited similar catalytic activity in case of reductions of diphenylacetylene and nitrobenzene, Pd@CF2 predominantly promoted the reduction of p-nitrobenzaldehyde to p-aminobenzyl alcohol whereas Pd/C gave p-toluidine. The reduction of p-dinitrobenzene led to predominant formation of p-nitrophenylhydroxylamine if promoted by the novel catalyst and to a mixture of products if promoted by Pd/C. In addition, the introduction of p-alkoxy groups onto nitrobenzenes slowed down the reduction with Pd@CF2 but had no influence on Pd/C activity. A hypothesis ascribing these observations to dissimilar equilibrium distributions of nitro and polar groups within the organic framework and the palladium metal surface is proposed to rationalize the selectivity of the novel catalytic material.

Kuznetsova S.A. , Yunusov S.M. , North M. , Zhereb V.P. , Khakina E.A. , Naumkin A. , Lobanov N.N. , Khrustalev V.N. , Chusov D. , Kalyuzhnaya E.S. , Ilyin M.M. , Morozov V.V. , Kashin A.S. , Ezernitskaya M.G. , Belokon Y.N.
Chiral Organic Salt Supported Pd Nanoparticles as Selective Heterogeneous Catalysts of Hydrogenation Reactions
ChemistrySelect. 2024. V.9. N41. e202402788 . DOI: 10.1002/slct.202402788 WOS Scopus OpenAlex

≡ Web of science:	WOS:001353366500001
≡ Scopus:	2-s2.0-85208034780
≡ OpenAlex:	W4403872007