Mechanistic Insight into Heterogeneous Hydrogenation of Furan Derivatives with the Use of Parahydrogen | Sciact - CRIS-система Института катализа

Mechanistic Insight into Heterogeneous Hydrogenation of Furan Derivatives with the Use of Parahydrogen Научная публикация

Журнал

ChemCatChem
ISSN: 1867-3880 , E-ISSN: 1867-3899

Вых. Данные

Год: 2018, Том: 10, Номер: 5, Страницы: 1178-1183 Страниц : 6 DOI: 10.1002/cctc.201701653

Ключевые слова

Hydrogenation, Oxygen heterocycles, Polarization, Reaction mechanisms, Supported catalysts

Авторы

Salnikov Oleg G. ^1,2 , Kovtunova Larisa M. ^2,3 , Skovpin Ivan V. ^1,2 , Bukhtiyarov Valerii I. ^2,3 , Kovtunov Kirill V. ^1,2 , Koptyug Igor V. ^1,2

Организации

1	Laboratory of Magnetic Resonance Microimaging International Tomography Center, SB RAS 3A Institutskaya st., Novosibirsk 630090, Russia
2	Novosibirsk State University 2 Pirogova st., Novosibirsk 630090, Russia
3	Laboratory of Surface Science Boreskov Institute of Catalysis, SB RAS 5 Acad. Lavrentiev pr., Novosibirsk 630090, Russia

Информация о финансировании (4)

1	Федеральное агентство научных организаций России	0303-2016-0004
2	Российский научный фонд	17-73-20030
3	Российский фонд фундаментальных исследований	16-33-60198
4	Федеральное агентство научных организаций России	0333-2017-0002

Parahydrogen-induced polarization (PHIP) was shown to be a useful and unique technique for mechanistic studies of catalytic reactions involving hydrogen. In this paper, PHIP was utilized for mechanistic investigation of gas phase hydrogenation of furan, 2,3-dihydrofuran and 2,5-dihydrofuran over titania-supported Rh, Pd and Pt catalysts. In hydrogenations of all three substrates over Rh/TiO2 catalysts, PHIP technique revealed the possibility of pairwise addition of two H atoms from the same H2 molecule with formation of tetrahydrofuran molecules while retaining spin correlation between added protons. In hydrogenation of 2,3-dihydrofuran over Rh/TiO2 catalysts, PHIP effects were detected not only for tetrahydrofuran but also for the reactant (2,3-dihydrofuran) at positions 2 and 3 of heterocyclic ring. Such unexpected results are a direct evidence of the occurrence of pairwise replacement of hydrogen atoms in 2,3-dihydorfuran. The probable mechanism of this pairwise replacement includes the sequential steps of addition and elimination of hydrogen atoms. In contrast, when hydrogenation of 2,5-dihydrofuran was carried out over Rh/TiO2, PHIP effects were detected for all protons of 2,3-dihydrofuran, implying that 2,3-dihydrofuran can be formed from 2,5-dihydrofuran not only via isomerization of C=C bond but also via dehydrogenation of 2,5-dihydrofuran to furan with subsequent semihydrogenation.

Salnikov O.G. , Kovtunova L.M. , Skovpin I.V. , Bukhtiyarov V.I. , Kovtunov K.V. , Koptyug I.V.
Mechanistic Insight into Heterogeneous Hydrogenation of Furan Derivatives with the Use of Parahydrogen
ChemCatChem. 2018. V.10. N5. P.1178-1183. DOI: 10.1002/cctc.201701653 WOS Scopus РИНЦ CAPlus OpenAlex

Поступила в редакцию:	16 окт. 2017 г.
Принята к публикации:	7 нояб. 2017 г.
Опубликована online:	5 февр. 2018 г.
Опубликована в печати:	7 мар. 2018 г.

Web of science:	WOS:000426844600042
Scopus:	2-s2.0-85041602872
РИНЦ:	35514594
Chemical Abstracts:	2018:215396
OpenAlex:	W2767252494

БД	Цитирований
Web of science	19
Scopus	20
РИНЦ	18
OpenAlex	26