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Scavenger-Based Immobilized Rh and Ir Complexes in Hydrogenation of Propyne and Propene with Parahydrogen Review

Journal Applied Magnetic Resonance
ISSN: 0937-9347 , E-ISSN: 1613-7507
Output data Year: 2024, Volume: 55, Pages: 1275–1291 Pages count : 17 DOI: 10.1007/s00723-024-01660-0
Tags Catalysts; Iridium compounds; Metal nanoparticles; Nuclear magnetic resonance spectroscopy; Propylene; Rhodium compounds; Silica gel; Thermodynamic stability; X ray photoelectron spectroscopy
Authors Skovpin Ivan V. 1 , Burueva Dudari B. 1 , Kovtunova Larisa M. 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, Russia 630090
2 Boreskov Institute of Catalysis SB RAS, 5 Lavrentieva Pr., Novosibirsk, Russia 630090

Funding (2)

1 Russian Science Foundation 22-43-04426
2 Ministry of Science and Higher Education of the Russian Federation FWUR-2024-0032

Abstract: The immobilization of dimeric [M2(COD)2(μ–Cl)2] complexes (M – Rh or Ir) by the interaction with -SH groups of 3-mercaptopropyl-functionalized silica gel leads to RhCl–S–SiO2 and IrCl–S–SiO2 catalysts active in hydrogenations of propene and propyne. Nuclear magnetic resonance enhancement in parahydrogen-induced polarization experiments was studied in a wide range of hydrogenations conditions (25–120 °C, 1.0–3.9 bar). The structural transformations were studied using ex situ X-ray photoelectron spectroscopy (XPS). It was established that IrCl–S–SiO2 demonstrated greater thermal stability in the hydrogenation of both propene and propyne in comparison with RhCl–S–SiO2. The beneficial effect of propyne was elucidated for thermal stability of studied catalysts and for the efficiency of the pairwise hydrogen addition. This can be explained by more efficient binding of the C≡C triple bond to an active center. The increase in reaction pressure typically leads to higher conversion in hydrogenations for both catalysts, but also decreases the temperatures sufficient for the reduction of anchored complexes with the formation of metal nanoparticles, which was confirmed by XPS.
Cite: Skovpin I.V. , Burueva D.B. , Kovtunova L.M. , Nartova A.V. , Kvon R.I. , Bukhtiyarov V.I. , Koptyug I.V.
Scavenger-Based Immobilized Rh and Ir Complexes in Hydrogenation of Propyne and Propene with Parahydrogen
Applied Magnetic Resonance. 2024. V.55. P.1275–1291. DOI: 10.1007/s00723-024-01660-0 WOS Scopus РИНЦ AN OpenAlex
Dates:
Submitted: Mar 12, 2024
Accepted: May 13, 2024
Published online: May 22, 2024
Published print: Oct 1, 2024
Identifiers:
Web of science: WOS:001229233100001
Scopus: 2-s2.0-85193855473
Elibrary: 67619882
Chemical Abstracts: 2024:1303086
OpenAlex: W4398215915
Citing:
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OpenAlex 1
Scopus 1
Web of science 1
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