Highly selective hydroformylation of internal and terminal olefins to terminal aldehydes using a rhodium-BIPHEPHOS-catalyst system

Vogl, C.; Paetzold, Eckhard; Fischer, Christine; Kragl, Udo

doi:10.1016/j.molcata.2005.01.019

Cited by 62 publications

(31 citation statements)

References 15 publications

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“…Obviously, tridecanal is the main reaction product especially at elevated temperatures and pressures. Thus, the reversible isomerization reaction (r iso ) and the consecutive hydroformylation (r hf,b ) occur as discussed also in (Behr et al, 2003;Vogl et al, 2005). Due to the high relative activation energy of the isomerization E A,iso the influence of this reaction is particularly significant at elevated temperature as already mentioned above.…”

Section: Sub-network Iv-hydroformylation Of Iso-dodecene (R Hfa )mentioning

confidence: 79%

“…1). The same uncertainty remains regarding the two ways possible to form the small amount of observed iso-aldehyde considering a possible backisomerization by the reversible reaction r iso followed by r hf,c (Behr et al, 2005b;Vogl et al, 2005).…”

Section: Illustration Of Transients In the Complete Reaction Systemmentioning

confidence: 99%

“…8b the series reaction of isododecene to dodecane takes place. However, a coupled mechanism of back-isomerization to 1-dodecene by r iso and subsequent hydrogenation to dodecane by r hg,b is imaginable (Vogl et al, 2005).…”

Section: Sub-network Iii-hydrogenation Of 1-dodecene (R Hgb )mentioning

confidence: 99%

See 2 more Smart Citations

Kinetics of 1-dodecene hydroformylation in a thermomorphic solvent system using a rhodium-biphephos catalyst

Kiedorf

Hoang

Müller

et al. 2014

Chemical Engineering Science

138

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Section: Sub-network Iv-hydroformylation Of Iso-dodecene (R Hfa )mentioning

confidence: 79%

Section: Illustration Of Transients In the Complete Reaction Systemmentioning

confidence: 99%

See 1 more Smart Citation

Kinetics of 1-dodecene hydroformylation in a thermomorphic solvent system using a rhodium-biphephos catalyst

Kiedorf

Hoang

Müller

et al. 2014

Chemical Engineering Science

138

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“…However, the polymer supported catalyst is not as active or regioselective as the BiPhePhos ligated catalyst. In addition, our catalyst hydroformylates the internal olefin 2-octene to produce mainly branched aldehyde, while BiPhePhos catalyzes the isomerizationhydroformylation of internal octenes to give w-aldehydes (20). Rh(acac)(CO) 2 (0.0067 mmol), 1-octene (6.7 mmol), in toluene (2.5 mL) at 60 °C for lh.…”

Section: Methodsmentioning

confidence: 99%

Hydroformylation in CO₂-Expanded Media

Wang

Cai

Jin

et al. 2009

Gas-Expanded Liquids and Near-Critical Media

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“…Conversions up to 99% and yields up to 86% of the aldehydes (linear : branched ratio 99 : 1) were found. A very high TOF of 44 000 h À1 was achieved at 140 C and 30 bar CO : H 2 ¼ 1 : 1 using a rhodium-to-1-dodecene ratio of 1 : 100 000 [48]. An efficient product and catalyst separation was achieved by the application of a temperature-dependent multicomponent solvent (TMS) system in rhodium-BIPHEPHOS catalyzed hydroformylation of trans-4-octene to n-nonanal.…”

mentioning

confidence: 99%

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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Highly selective hydroformylation of internal and terminal olefins to terminal aldehydes using a rhodium-BIPHEPHOS-catalyst system

Cited by 62 publications

References 15 publications

Kinetics of 1-dodecene hydroformylation in a thermomorphic solvent system using a rhodium-biphephos catalyst

Kinetics of 1-dodecene hydroformylation in a thermomorphic solvent system using a rhodium-biphephos catalyst

Hydroformylation in CO₂-Expanded Media

Carbonylation of Alkenes and Dienes

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Highly selective hydroformylation of internal and terminal olefins to terminal aldehydes using a rhodium-BIPHEPHOS-catalyst system

Cited by 62 publications

References 15 publications

Kinetics of 1-dodecene hydroformylation in a thermomorphic solvent system using a rhodium-biphephos catalyst

Kinetics of 1-dodecene hydroformylation in a thermomorphic solvent system using a rhodium-biphephos catalyst

Hydroformylation in CO2-Expanded Media

Carbonylation of Alkenes and Dienes

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Hydroformylation in CO₂-Expanded Media