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

IF 1.1 4区 物理与天体物理 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL Applied Magnetic Resonance Pub Date : 2024-05-22 DOI:10.1007/s00723-024-01660-0
Ivan V. Skovpin, Dudari B. Burueva, Larisa M. Kovtunova, Anna V. Nartova, Ren I. Kvon, Valerii I. Bukhtiyarov, Igor V. Koptyug
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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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丙炔和丙烯与对氢的加氢反应中基于清除剂的固定化 Rh 和 Ir 复合物
二聚[M2(COD)2(μ-Cl)2]复合物(M - Rh 或 Ir)通过与 3-巯基丙基官能化硅胶的 -SH 基团相互作用而固定化,从而产生了在丙烯和丙炔加氢反应中具有活性的 RhCl-SiO2 和 IrCl-SiO2 催化剂。在广泛的氢化条件(25-120 °C,1.0-3.9 巴)下研究了对氢诱导极化实验中核磁共振的增强。利用原位 X 射线光电子能谱 (XPS) 研究了结构转变。结果表明,与 RhCl-SiO2 相比,IrCl-S-SiO2 在丙烯和丙炔的氢化过程中表现出更高的热稳定性。丙炔对所研究催化剂的热稳定性和成对氢加成效率的有利影响得到了阐明。这可以用 C≡C 三键与活性中心的更有效结合来解释。增加反应压力通常会提高两种催化剂的加氢转化率,但同时也会降低锚定络合物还原所需的温度,从而形成金属纳米颗粒,这一点已由 XPS 证实。
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来源期刊
Applied Magnetic Resonance
Applied Magnetic Resonance 物理-光谱学
CiteScore
1.90
自引率
10.00%
发文量
59
审稿时长
2.3 months
期刊介绍: Applied Magnetic Resonance provides an international forum for the application of magnetic resonance in physics, chemistry, biology, medicine, geochemistry, ecology, engineering, and related fields. The contents include articles with a strong emphasis on new applications, and on new experimental methods. Additional features include book reviews and Letters to the Editor.
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