An X-ray Photoelectron Spectroscopy Study of Variations in the Stability of [M(COD)Cl]2 (M = Ir, Rh) Complexes Anchored on Modified Silica in the Spin-Selective Hydrogenation of Unsaturated Hydrocarbons with Parahydrogen

IF 1.3 4区化学 Q4 CHEMISTRY, PHYSICAL

Kinetics and Catalysis Pub Date : 2024-05-09 DOI:10.1134/S0023158423601213

A. V. Nartova, R. I. Kvon, L. M. Kovtunova, A. M. Dmitrachkov, I. V. Skovpin, V. I. Bukhtiyarov

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Abstract

Changes in the composition of immobilized [M(COD)Cl]₂–NH₂–C₃H₆–SiO₂ and [M(COD)Cl]₂–P(Ph)₂–C₂H₄–SiO₂ (where M = Ir, Rh) catalysts in the gas-phase selective hydrogenation of propylene, propyne, and 1,3-butadiene with parahydrogen (p-H₂) have been studied by the XPS method. It has been proposed that the M/Cl atomic ratio should be used as an indicator of the structural stability of the anchored complex both at the sample synthesis stage and in the reaction. Based on comparison of XPS data and results of catalytic tests using parahydrogen-induced nuclear polarization, it has been shown that the stability of the anchored {[M(COD)Cl]₂–Linker–SiO₂} complex during hydrogen activation is a key factor in the catalytic behavior of the systems. The stability of the complex is affected not only by the chosen metal and linker, but also by the nature of the substrate subjected to hydrogenation.

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X 射线光电子能谱对锚定在改性二氧化硅上的 [M(COD)Cl]2（M = Ir、Rh）配合物在不饱和碳氢化合物与对氢的自旋选择性加氢反应中稳定性变化的研究

摘要利用 XPS 方法研究了固定化 [M(COD)Cl]2-NH2-C3H6-SiO2 和 [M(COD)Cl]2-P(Ph)2-C2H4-SiO2（其中 M = Ir、Rh）催化剂在丙烯、丙炔和 1,3-丁二烯与对氢（p-H2）的气相选择性加氢反应中的组成变化。有人提出，在样品合成阶段和反应过程中，M/Cl 原子比应作为锚定复合物结构稳定性的指标。根据 XPS 数据与使用对氢诱导核极化进行的催化测试结果的比较，结果表明锚定 {[M(COD)Cl]2-Linker-SiO2} 复合物在氢活化过程中的稳定性是影响系统催化行为的关键因素。复合物的稳定性不仅受所选金属和连接体的影响，还受氢化底物性质的影响。

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来源期刊

Kinetics and Catalysis 化学-物理化学

CiteScore

2.10

自引率

27.30%

发文量

审稿时长

6-12 weeks

期刊介绍： Kinetics and Catalysis Russian is a periodical that publishes theoretical and experimental works on homogeneous and heterogeneous kinetics and catalysis. Other topics include the mechanism and kinetics of noncatalytic processes in gaseous, liquid, and solid phases, quantum chemical calculations in kinetics and catalysis, methods of studying catalytic processes and catalysts, the chemistry of catalysts and adsorbent surfaces, the structure and physicochemical properties of catalysts, preparation and poisoning of catalysts, macrokinetics, and computer simulations in catalysis. The journal also publishes review articles on contemporary problems in kinetics and catalysis. The journal welcomes manuscripts from all countries in the English or Russian language.