The PPh3 ligand modified Rh/SiO2 catalyst for hydroformylation of olefins

Zhu, Huichao; Ding, Yunjie; Li, Yan; Xiong, Jianmin; Lü, Yuan; Lin, Liwu

doi:10.1016/j.cattod.2004.06.082

Cited by 20 publications

(9 citation statements)

References 15 publications

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“…It can be seen an important increase of % weight loss according with the amount of (S,S)-DIPAMP added in the NPs synthesis, indicative of the chiral ligand is on catalysts surface. Decomposition around 500 °C is indicating that there is likely a chemical interaction between (S,S)-DIPAMP and Rh/SiO 2 , as shown previous reports 36 . No visible diffraction lines attributable to rhodium crystalline phase of Rh-(x)L/Si catalysts appeared in XRD patterns, due to Rh has small particle diameter and the metal loading in these catalysts were was 1% wt of rhodium.…”

Section: Catalysts Characterizationsupporting

confidence: 85%

CHIRAL Rh/SiO2 CATALYSTS FOR ENANTIOSELECTIVE HYDROGENATION REACTIONS: THE ROLE OF (S,S)-DIPAMP AS CHIRAL MODIFIER AND STABILIZER ON METALLIC NANOPARTICLES SYNTHESIS

Mella¹,

Ávila²,

SANCHEZ³

et al. 2013

J. Chil. Chem. Soc.

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Rhodium nanoparticles were successfully stabilized by the (S,S)-1,2-ethanediylbis [(2-ethoxyphenyl)phenylphosphine] ((S,S)-DIPAMP) deposited on SiO 2 prepared by a facile reduction and impregnation method. The chiral catalysts obtained were efficient for the enantioselective hydrogenation reactions of prochiral compounds. The catalysts synthesized from [Rh(μ-OMe)(COD)] 2 in the presence of different amounts of a ligand used as chiral stabilizer, showed good metal dispersion. As shown by TEM, the metal particle size ranged between 1 and 2 nm using stabilizer and 9.1 nm was achieved without chiral ligand. Other techniques were used to characterize the chiral catalysts such as X-ray diffraction (XRD), electron diffraction, thermogravimetric analysis (TGA) and N 2 adsorption-desorption isotherms.(S,S)-DIPAMP was used as the stabilizer of metal particles to prevent growing and agglomeration, and it also acts as chiral modifier inducing enantioselectivity in the asymmetric hydrogenation of 3,4-hexanodione (HD), ethyl pyruvate (EP), ketopantolactone (KP), and acetophenone (AP). Under specific conditions such as 25 °C, 40 bar of H 2 and substrate/Rh=100, 1%Rh-(S,S)-DIPAMP/SiO 2 chiral catalysts showed excellent catalytic performance with conversion and enantiomeric excess (ee) levels up to 99% and 54% respectively.

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Section: Catalysts Characterizationsupporting

confidence: 85%

CHIRAL Rh/SiO2 CATALYSTS FOR ENANTIOSELECTIVE HYDROGENATION REACTIONS: THE ROLE OF (S,S)-DIPAMP AS CHIRAL MODIFIER AND STABILIZER ON METALLIC NANOPARTICLES SYNTHESIS

Mella¹,

Ávila²,

SANCHEZ³

et al. 2013

J. Chil. Chem. Soc.

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“…Ding and co-workers have reported a different approach for producing an active catalyst for propene hydroformylation. In this case, silica-supported Rh nanoparticles are promoted with PPh 3 , 13,14 and Kim et al have recently shown that the highest activity for PPh 3 -modified Rh/SiO 2 is achieved for PPh 3 /Rh = 15. 15 Because of the similarities in activation energies, partial and total pressure dependences of the reaction rates for PPh 3modified Rh/SiO 2 and homogeneous HRh(CO)(PPh 3 ) 3 catalysts suggest that the active species in both systems are identical.…”

Section: Introductionmentioning

confidence: 99%

In Situ Formation of Wilkinson-Type Hydroformylation Catalysts: Insights into the Structure, Stability, and Kinetics of Triphenylphosphine- and Xantphos-Modified Rh/SiO₂

et al. 2013

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An investigation has been carried out to identify the effects of catalyst preparation on the activity, selectivity, and stability of phosphine-modified rhodium/silica catalysts (Rh/SiO2) for propene hydroformylation. High selectivity to aldehydes was achieved, without the formation of propane or butanol. Catalyst activity and selectivity was found to depend strongly on the nature and concentration of the phosphine ligands and the amount of rhodium dispersed on the silica support. Screening of different ligands showed that a bidentate xantphos (X) ligand was ∼2-fold more active than the monodentate phosphine ligand (PPh3) screened at a ligand-to-rhodium ratio of 15:1. Investigation of the effects of reaction temperature, reactant partial pressures, and phosphine-to-rhodium ratio indicates that the kinetics of propene hydroformylation over X-promoted Rh/SiO2 is nearly identical to those for sulfoxantphos-modified rhodium-containing supported ionic liquid phase (SX-Rh SILP) catalysts. In-situ FTIR and solid-state 31P MAS NMR characterization provide evidence for the formation of HRh(CO) n (PPh3)4–n species on PPh3-modified Rh/SiO2, and HRh(CO)2(X) species on xantphos-modified Rh/SiO2. The high catalytic activity observed over rhodium-containing silica catalysts is attributed to formation of Rh(I)(CO)2 species by the process of corrosive chemisorption of Rh nanoparticles by CO and the subsequent ligation of phosphine ligands to the dicarbonyl species. Evidence is also presented suggesting that the active form of the catalyst resides on the surface of the Rh nanoparticles.

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“…[6][7][8] The electron donor-acceptor properties of phosphine ligands in homogeneous catalysis system have been studied on the basis of the correlation of IR frequencies of the co-coordinated CO. 1,9 More recently, Rh/SiO 2 catalyst modified with PPh 3 , one of the most widely used phosphine ligands, was used in heterogeneous hydroformylation of olefin. [10][11][12][13] Compared with the conventional homogeneous hydroformylation, the heterogeneous catalytic process has several merits, for example, the catalyst can be easily separated from the reaction system and can be recyclable. Also, these merits will lead to the possibility for the application of the catalyst in industry.…”

Section: Introductionmentioning

confidence: 99%

Charge Transfer between Triphenyl Phosphine and Colloidal Silver: A SERS Study Combined with DFT Calculations

Feng

Han

et al. 2007

J. Phys. Chem. C

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The adsorption of triphenyl phosphine (PPh3) on colloidal silver has been investigated by means of surface-enhanced Raman spectroscopy (SERS). On the basis of surface selection rule, it is deduced from SERS results that PPh3 adsorbs on silver surface via its P atom with three phenyl rings tilted with respect to the silver surface. The electron-donor effect of PPh3 can be sensitively probed by the coadsorbed SCN-. The Raman frequency of νCN of the adsorbed SCN- shifts to lower frequencies when PPh3 is coadsorbed with SCN-, and the red shift of C⋮N stretching frequency is found to increase with increasing the surface coverage of PPh3. This could be explained in terms of the electron-donor effect of PPh3: PPh3 adsorbed on silver surface donates its lone pair of electrons to silver surface, and then the negative charge of silver surface transfers to the π* orbital of C⋮N bond via S−Ag bond. Consequently, the C⋮N bond is weakened, and the frequency of νCN shifts to lower frequencies. Density functional theory (DFT) calculations further confirm the experimental results that the charge transfer is from PPh3 to silver surface rather than reversely. The information obtained from the adsorption of PPh3 on silver by SERS may be helpful to understand the mechanism of heterogeneous catalysis involving phosphine ligands coordinated on transition-metal surfaces.

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The PPh3 ligand modified Rh/SiO2 catalyst for hydroformylation of olefins

Cited by 20 publications

References 15 publications

CHIRAL Rh/SiO2 CATALYSTS FOR ENANTIOSELECTIVE HYDROGENATION REACTIONS: THE ROLE OF (S,S)-DIPAMP AS CHIRAL MODIFIER AND STABILIZER ON METALLIC NANOPARTICLES SYNTHESIS

CHIRAL Rh/SiO2 CATALYSTS FOR ENANTIOSELECTIVE HYDROGENATION REACTIONS: THE ROLE OF (S,S)-DIPAMP AS CHIRAL MODIFIER AND STABILIZER ON METALLIC NANOPARTICLES SYNTHESIS

In Situ Formation of Wilkinson-Type Hydroformylation Catalysts: Insights into the Structure, Stability, and Kinetics of Triphenylphosphine- and Xantphos-Modified Rh/SiO₂

Charge Transfer between Triphenyl Phosphine and Colloidal Silver: A SERS Study Combined with DFT Calculations

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The PPh3 ligand modified Rh/SiO2 catalyst for hydroformylation of olefins

Cited by 20 publications

References 15 publications

CHIRAL Rh/SiO2 CATALYSTS FOR ENANTIOSELECTIVE HYDROGENATION REACTIONS: THE ROLE OF (S,S)-DIPAMP AS CHIRAL MODIFIER AND STABILIZER ON METALLIC NANOPARTICLES SYNTHESIS

CHIRAL Rh/SiO2 CATALYSTS FOR ENANTIOSELECTIVE HYDROGENATION REACTIONS: THE ROLE OF (S,S)-DIPAMP AS CHIRAL MODIFIER AND STABILIZER ON METALLIC NANOPARTICLES SYNTHESIS

In Situ Formation of Wilkinson-Type Hydroformylation Catalysts: Insights into the Structure, Stability, and Kinetics of Triphenylphosphine- and Xantphos-Modified Rh/SiO2

Charge Transfer between Triphenyl Phosphine and Colloidal Silver: A SERS Study Combined with DFT Calculations

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In Situ Formation of Wilkinson-Type Hydroformylation Catalysts: Insights into the Structure, Stability, and Kinetics of Triphenylphosphine- and Xantphos-Modified Rh/SiO₂