Ionic Liquids in Transition Metal-Catalyzed Hydroformylation Reactions

The first, recyclable protocol for the selective synthesis of (E)-alkenyl boronates via borylative coupling of olefins with vinylboronic acid pinacol ester in monophasic (cat@IL) or biphasic (cat@IL/scCO2) systems is reported in this article. The efficient immobilization of [Ru(CO)Cl(H)(PCy3)2] (1 mol%) in [EMPyr][NTf2] and [BMIm][OTf] with the subsequent extraction of products with n-heptane permitted multiple reuses of the catalyst without a significant decrease in its activity and stability (up to 7 runs). Utilization of scCO2 as an extractant enabled a significant reduction in the amount of catalyst leaching during the separation process, compared to extraction with n-heptane. Such efficient catalyst immobilization allowed an intensification of the processes in terms of its productivity, which was indicated by high cumulative TON values (up to 956) in contrast to the traditional approach of applying volatile organic solvents (TON = ~50–100). The reaction was versatile to styrenes with electron-donating and withdrawing substituents and vinylcyclohexane, generating unsaturated organoboron compounds, of which synthetic utility was shown by the direct transformation of extracted products in iododeborylation and Suzuki coupling processes. All synthesized compounds were characterized using 1H, 13C NMR and GC-MS, while leaching of the catalyst was detected with ICP-MS.

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“…NMR and GC-MS data are in agreement with the literature [29]. (11), 171 (19), 155 (15), 143 (23), 129 (9), 83 (10), 57 (13). Isolated yield: 73%.…”

Section: Iododeborylation Of 3a With Molecular Iodinesupporting

confidence: 89%

“…(E)-2-(4'-Bromostyryl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3b), 1 H NMR (300 MHz, acetone-d 6 , 25 (9), 175 (11), 162(73), 148(100), 136 (21), 123 (23), 102 (13), 85 (19), 57 (14). Isolated yield: 78%.…”

Section: Iododeborylation Of 3a With Molecular Iodinementioning

confidence: 99%

Ru-Catalyzed Repetitive Batch Borylative Coupling of Olefins in Ionic Liquids or Ionic Liquids/scCO2 Systems

et al. 2020

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“…In the process, the products are easily separated from the reactive ionic catalyst phase and the metal catalyst and ILs are recycled without applying any thermal stress to the ionic catalyst solution . The typical biphasic reactions are hydrogenation reaction, − dimerization reaction, , and hydroformylation reactions. , In the hydrogenation of cyclohexene by RhCl(TPP) 3 catalyst, it was found that the rates of hydrogenation in [C 4 C 1 im][SbF 6 ] are almost five times faster than those in acetone, and the ILs can be reused repeatedly and the loss of rhodium leaching into the organic phase was below 0.02% . In the hydroformylation of 1-octene reaction, the imidazolium-based dicationic phenoxaphosphino-modified xantphos-type ligand was used in [C 4 C 1 im][PF 6 ] IL .…”

Section: Unit Scale Design Based On Ils Mediamentioning

confidence: 99%

Multiscale Studies on Ionic Liquids

et al. 2017

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Ionic liquids (ILs) offer a wide range of promising applications because of their much enhanced properties. However, further development of such materials depends on the fundamental understanding of their hierarchical structures and behaviors, which requires multiscale strategies to provide coupling among various length scales. In this review, we first introduce the structures and properties of these typical ILs. Then, we introduce the multiscale modeling methods that have been applied to the ILs, covering from molecular scale (QM/MM), to mesoscale (CG, DPD), to macroscale (CFD for unit scale and thermodynamics COSMO-RS model and environmental assessment GD method for process scale). In the following section, we discuss in some detail their applications to the four scales of ILs, including molecular scale structures, mesoscale aggregates and dynamics, and unit scale reactor design and process design and optimization of typical IL applications. Finally, we address the concluding remarks of multiscale strategies in the understanding and predictive capabilities of ILs. The present review aims to summarize the recent advances in the fundamental and application understanding of ILs.

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“…In the last few decades, a number of research activities in academia and industry have focused on the conceptual development of heterogeneous or heterogenized hydroformylation catalysts. Among other rhodium complexes, pure or ligand-modified rhodium nanoparticles immobilized on inorganic support materials were tested as catalysts. − Aside from compromises with regard to lower turnover frequencies (TOFs) observed compared to homogeneous catalyst analogues, it could also be shown that the reaction is likely catalyzed by molecular rhodium species being present in pseudoliquid films on the catalyst surface. − A topic that has attracted a lot of attention is the supported ionic liquid phase (SILP) process where the catalyst is dissolved in an ionic liquid that is supported on a specific support material. − Compared to other heterogenized catalysts, the reported TOF values are initially high but drop over time. The reason for this decline in activity is due to the formation of condensation products that accumulate in the ionic liquid and poison the catalyst.…”

Section: Introductionmentioning

confidence: 99%

Platinum Group Metal Phosphides as Heterogeneous Catalysts for the Gas-Phase Hydroformylation of Small Olefins

Rupflin¹,

Mormul²,

Lejkowski³

et al. 2017

ACS Catal.

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A method for the synthesis of highly crystalline Rh₂P nanoparticles on SiO₂ support materials and their use as truly eterogeneous single-site catalysts for the hydroformylation of ethylene and propylene is presented. The supported Rh₂P nanoparticles were investigated by transmission electron microscopy and by infrared analysis of adsorbed CO. The influence of feed gas composition and reaction temperature on the activity and selectivity in the hydroformylation reaction was evaluated by using high throughput experimentation as an enabling element; core findings were that beneficial effects on the selectivity were observed at high CO partial pressures and after addition of water to the feed gas. The analytical and performance data of the materials gave evidence that high temperature reduction leading to highly crystalline Rh₂P nanoparticles is key to achieving active, selective, and longterm stable catalysts

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Ionic Liquids in Transition Metal-Catalyzed Hydroformylation Reactions

Cited by 8 publications

References 171 publications

Ru-Catalyzed Repetitive Batch Borylative Coupling of Olefins in Ionic Liquids or Ionic Liquids/scCO2 Systems

Ru-Catalyzed Repetitive Batch Borylative Coupling of Olefins in Ionic Liquids or Ionic Liquids/scCO2 Systems

Multiscale Studies on Ionic Liquids

Platinum Group Metal Phosphides as Heterogeneous Catalysts for the Gas-Phase Hydroformylation of Small Olefins

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