Anchored Complexes of Rhodium and Iridium for the Hydrogenation of Alkynes and Olefins with Parahydrogen
Научная публикация
| Общая информация |
Язык:
Английский,
Жанр:
Статья (Full article),
Статус опубликования:
Опубликована,
Оригинальность:
Оригинальная
|
| Журнал |
Catalysis Science and Technology
ISSN: 2044-4753
, E-ISSN: 2044-4761
|
| Вых. Данные |
Год: 2022,
Том: 12,
Номер: 10,
Страницы: 3247-3253
Страниц
: 7
DOI:
10.1039/d1cy02258j
|
| Ключевые слова |
Catalyst activity; Gases; Hydrogenation; Iridium compounds; Metal complexes; Nuclear magnetic resonance; Phosphorus compounds; Propylene; Rhodium compounds; Silica gel; Synthesis (chemical) |
| Авторы |
Skovpin Ivan V.
1
,
Kovtunova Larisa M.
1,2
,
Nartova Anna V.
2
,
Kvon Ren I.
2
,
Bukhtiyarov Valerii I.
2
,
Koptyug Igor V.
1
|
| Организации |
| 1 |
International Tomography Center, SB RAS, 3A Institutskaya St., Novosibirsk, 630090, Russian Federation
|
| 2 |
Boreskov Institute of Catalysis, SB RAS, 5 Acad. Lavrentiev Pr., Novosibirsk, 630090, Russian Federation
|
|
Информация о финансировании (3)
|
1
|
Российский фонд фундаментальных исследований
|
19-29-10003 (АААА-А19-119100890052-8)
|
|
2
|
Министерство науки и высшего образования Российской Федерации
|
0239-2021-0002
|
|
3
|
Министерство науки и высшего образования Российской Федерации
|
|
Several catalysts synthesized by covalently binding Rh and Ir complexes to NH2- and PPh2- functional groups of the linker chains on the functionalized silica gel surface were compared in gas-phase hydrogenation of propyne and propene. Their stability, activity and product selectivity were evaluated. Furthermore, the use of parahydrogen in the reaction provided useful mechanistic information by delivering nuclear spin hyperpolarization of the reaction products with the associated enhancement of their NMR signals. In contrast to Rh-based catalysts which showed a pronounced tendency to reduction, for Ir-based catalysts an XPS analysis did not reveal any indication of the formation of a metal phase under reducing conditions upon hydrogenation of propyne or propene at 120 °C. Catalysts with a π-acceptor ligand PPh2- demonstrated greater activity in the gas-phase hydrogenation of propyne/propene in comparison with σ-donor ligand NH2-. Furthermore, NMR signal enhancements of up to ca. 700- (Rh) and 800-fold (Ir) were achieved. Remarkably, the Ir metal complex bound via the phosphine moiety demonstrated high stability in gas-phase hydrogenation of propyne along with high catalytic activity and pairwise H2 addition selectivity, yielding substantial quantities of strongly hyperpolarized propene.