Hydroformylation of 1-hexene in supercritical carbon dioxide using a heterogeneous rhodium catalyst. 3. Evaluation of solvent effects

Hemminger, Orin; Marteel, Anne; Mason, Mark R.; Davies, Julian A.; Tadd, Andrew R.; Abraham, Martín

doi:10.1039/b204822c

Cited by 51 publications

(23 citation statements)

References 12 publications

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“…The enhanced rates and selectivity are attributed to increased syngas availability in the CXL phase. In contrast, the Rh complex-catalyzed hydroformylation of 1-hexene in C0 2 -expanded toluene was more rapid than in ^cC0 2 but slower than in normal toluene (67). The high C0 2 pressure was believed to dissolve some of the 1-hexene out of the liquid phase into the C0 2 phase, thereby lowering the concentration of hexene available to the catalyst.…”

Section: Homogeneous Catalysismentioning

confidence: 86%

Gas-Expanded Liquids: Fundamentals and Applications

Scurto

Hutchenson

Subramaniam

2009

Gas-Expanded Liquids and Near-Critical Media

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Section: Homogeneous Catalysismentioning

confidence: 86%

Gas-Expanded Liquids: Fundamentals and Applications

Scurto

Hutchenson

Subramaniam

2009

Gas-Expanded Liquids and Near-Critical Media

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“…Solvent effects on the kinetics of hydroformylation (HYFO) reactions have already been studied experimentally in conventional organic solvents, in supercritical carbon dioxide, and in ionic liquids. [2][3][4][5][6][7] It was shown that the use of different solvents can affect both, the reaction rate and the selectivity for the desired n-aldehyde. There is also consensus, that besides affecting the HYFO reaction, solvents also affect the solubility of the synthesis gas in the reaction mixture.…”

Section: Introductionmentioning

confidence: 99%

Predicting solvent effects on the 1‐dodecene hydroformylation reaction equilibrium

et al. 2017

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This work investigates solvent effects on the reaction equilibrium of the 1-dodecene hydroformylation in a decane/N,N-dimethylformamide solvent system. The reaction was performed at different decane/N,N-dimethylformamide ratios and at temperatures between 368 K and 388 K. The equilibrium concentrations of all reactants and products were determined experimentally. The enthalpy and Gibbs energy of this reaction at the ideal-gas standard state were determined by quantum-chemical calculations in good agreement with literature data. Moreover, quantum-chemically calculated standard Gibbs energies of reaction at infinite dilution in liquid decane/DMF-solvent mixtures allowed a qualitative prediction of the solvent effect on the equilibrium concentrations. Based on the standard Gibbs energy of reaction at the ideal-gas standard state and on fugacity coefficients calculated using the Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT), the equilibrium concentrations of reactants and products for the 1-dodecene hydroformylation performed in decane/N,N-dimethylformamide mixtures of different compositions could be predicted in very good agreement with experimental data.

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“…The performance of the tethered catalyst was compared with a homogeneous rhodium-phosphane catalyst and was found to be equally effective under identical reaction conditions. Initial aldehyde selectivity obtained with the heterogeneous species was also comparable to that obtained with the homogeneous catalyst, but it decreased over the course of the reaction [131]. Rhodium catalysts anchored on phosphinated silica-based supports were evaluated for their performance in the hydroformylation of 1-hexene in supercritical carbon dioxide.…”

Section: Hydroformylation In Supercritical Fluidsmentioning

confidence: 79%

Carbonylation of Alkenes and Dienes

Kégl

2008

Modern Carbonylation Methods

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In the beginning, only cobalt catalysts were utilized for hydroformylation under relatively vigorous conditions. The moderate selectivity of the generally more desired linear isomers, the substantial formation of by-products, and the low stability of the catalysts forced more appropriate catalytic systems to be developed. Using donor ligands such as phosphanes resulted in an increase in the linear selectivity. Rhodium-containing catalysts, however, permitted the use of much milder conditions in combination with suitable ligands. Other transition metals such as ruthenium, palladium, platinum, and iridium also tended to show activity for hydroformylation, albeit a vast majority of works on hydroformylation still concentrated on rhodium-containing systems. Cobalt CatalystsThe initial rate of Co 2 (CO) 8 -catalyzed cyclohexene hydroformylation, triethyl orthoformate carbonylation, and CoH(CO) 4 formation from Co 2 (CO) 8 and H 2 is reduced by the addition of dinitrogen, argon, or xenon. It is assumed that the additional gas competes with one or more reactants for a coordinatively unsaturated site responsible for their activation, thus affecting the reaction rate [1].The carbonylation reaction of propylene oxide in the presence of various [Lewis acid] þ [Co(CO) 4 ] À salts was investigated using in situ attenuated total reflection infrared (ATR-IR) spectroscopy. b-Alkoxy-acyl-cobalttetracarbonyl species were found to be key intermediates from which two reaction routes start depending on the applied Lewis acid. Labile Lewis acid-alkoxy combinations primarily favor the production of lactone products [2].The reaction of olefins (1-octene, 3,3-dimethylbutene, cyclohexene) introduced into a preequilibrated Co 2 (CO) 8 þ H 2 system was investigated by high-pressure infrared spectroscopy. Based on the observed induction period for the formation of the corresponding aldehyde, the decrease in HCo(CO) 4 concentration and increase in Co 2 (CO) 8 concentration during the induction period, the active catalytic species of the type H x Co y (CO) z was proposed [3]. Experiments with isotope mixtures of H 2 /D 2 in the gas phase during the various steps of the reaction showed that the ratio of H/D isotopes in the hydrocarbon portion of the aldehyde product correlates with the HCo(CO) 4 /DCo(CO) 4 ratio in solution, whereas the RC(¼O)H/RC(¼O)D product ratio correlates with the H 2 /D 2 in the gas phase. It was concluded that the dominant pathway for the hydrogenolysis step in this type of hydroformylation is the direct reaction of hydrogen or deuterium with the acyl complex intermediate [4].The effect of argon (280 bar) on the rate of aldehyde formation in 1-hexene hydroformylation catalyzed by Co 2 (CO) 8 at 50 C, 70 bar P(CO) and 85 bar P(H 2 ) in toluene was investigated by high-pressure FT-IR spectroscopy. The initial rate of the reaction was found to be reduced by the presence of argon. A similar effect was observed in the RhH(CO)(PPh 3 ) 3 -catalyzed cyclohexene hydroformylation reaction [5]. 162j 7 Carbonylation of Alkenes and D...

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Hydroformylation of 1-hexene in supercritical carbon dioxide using a heterogeneous rhodium catalyst. 3. Evaluation of solvent effects

Cited by 51 publications

References 12 publications

Gas-Expanded Liquids: Fundamentals and Applications

Gas-Expanded Liquids: Fundamentals and Applications

Predicting solvent effects on the 1‐dodecene hydroformylation reaction equilibrium

Carbonylation of Alkenes and Dienes

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