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

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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.

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Acknowledgements

I.V.S. and I.V.K. thank the Russian Science Foundation (grant #22-43-04426) for the support of PHIP experiments. The ITC team thanks the Ministry of Science and Higher Education of the Russian Federation for the access to NMR equipment. The BIC team of thanks (project FWUR-2024-0032) the Ministry of Science and Higher Education of the Russian Federation within the governmental order for the support of catalyst preparation and characterization.

Funding

The ITC team used funding of RSF (grant #22-43-04426) and the Ministry of Science and Higher Education of the Russian Federation (basic funding). The BIC team thanks (project FWUR-2024-0032) the Ministry of Science and Higher Education of the Russian Federation within the governmental order for the support of catalyst preparation and characterization.

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Authors and Affiliations

  1. International Tomography Center SB RAS, 3A Institutskaya St., Novosibirsk, Russia, 630090

    Ivan V. Skovpin, Dudari B. Burueva & Igor V. Koptyug

  2. Boreskov Institute of Catalysis SB RAS, 5 Lavrentieva Pr., Novosibirsk, Russia, 630090

    Larisa M. Kovtunova, Anna V. Nartova, Ren I. Kvon & Valerii I. Bukhtiyarov

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  1. Ivan V. Skovpin
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Contributions

I.V.K. supervised the work; L.M.K. contributed in catalyst preparation; A.V.N. and R.I.K characterized catalysts by XPS; I.V.S. and D.B.B. conducted the hydrogenation experiments; I.V.S. and D.B.B. wrote the original draft; I.V.K. and V.I.B. reviewed and edited the manuscript. The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.

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Correspondence to Igor V. Koptyug.

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Skovpin, I.V., Burueva, D.B., Kovtunova, L.M. et al. Scavenger-Based Immobilized Rh and Ir Complexes in Hydrogenation of Propyne and Propene with Parahydrogen. Appl Magn Reson (2024). https://doi.org/10.1007/s00723-024-01660-0

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