Anchored complexes of rhodium and iridium for the hydrogenation of alkynes and olefins with parahydrogen

Anchored complexes of rhodium and iridium for the hydrogenation of alkynes and olefins with parahydrogen Full article

Journal

Catalysis Science and Technology
ISSN: 2044-4753

Output data

Year: 2022, Volume: 12, Number: 10, Pages: 3247-3253 Pages count : 7 DOI: 10.1039/d1cy02258j

Authors

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

Affiliations

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

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.

Skovpin I.V. , Kovtunova L.M. , Nartova A.V. , Kvon R.I. , Bukhtiyarov V.I. , Koptyug I.V.
Anchored complexes of rhodium and iridium for the hydrogenation of alkynes and olefins with parahydrogen
Catalysis Science and Technology. 2022. V.12. N10. P.3247-3253. DOI: 10.1039/d1cy02258j WOS Scopus OpenAlex

Submitted:	Dec 14, 2021
Published online:	Mar 30, 2022
Published print:	May 21, 2022

Web of science:	WOS:000779872400001
Scopus:	2-s2.0-85129315196
OpenAlex:	W4225856904

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Scopus	19
Web of science	21