Ligand modified real heterogeneous catalysts for fixed-bed hydroformylation of propylene

Li, Yan; Ding, Yun; Zhu, He; Xiong, Jian; Wang, Tao; Pan, Zhen; Lin, Liwu

doi:10.1016/j.molcata.2005.01.047

Cited by 53 publications

(27 citation statements)

References 30 publications

(32 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The preparation of PPh 3 -Rh/SiO 2 catalysts followed previously described techniques [7][8][9][10][11][12]. 1 wt% Rh/SiO 2 was prepared by incipient wetness impregnation of mesoporous SiO 2 (Silicycle, 500 m 2 g -1 , average pore diameter 60 Å ) with a solution of rhodium (III) acetylacetonate (Aldrich, 97% pure) dissolved in toluene (Alfa Aesar, anhydrous 99.8% pure).…”

Section: Methodsmentioning

confidence: 99%

“…Also shown are the results for SiO 2 -and SBA-15-supported solutions of HRh(CO)(PPh 3 ) 3 in PPh 3 [8,11]. In all cases, except where sulfoxantphos was used, the PPh 3 /Rh ratio was 15.…”

Section: Catalytic Activity Of Pph 3 -Rh/siomentioning

confidence: 99%

“…The hydroformylation activity of the PPh 3 -Rh/SiO 2 catalyst prepared in this study is compared in Table 1 with those for similar catalysts prepared in which SiO 2 , MCF, and SBA-15 were used as supports [8,9,11,17]. Also shown are the results for SiO 2 -and SBA-15-supported solutions of HRh(CO)(PPh 3 ) 3 in PPh 3 [8,11].…”

Section: Catalytic Activity Of Pph 3 -Rh/siomentioning

confidence: 99%

“…In all cases, except where sulfoxantphos was used, the PPh 3 /Rh ratio was 15. Since the studies reported in [8,9,11,15] were done at 10 atm, we have used the observed dependence on total pressure for equimolar reactant mixtures, 3.1, to adjust the rate of butanal formation that we observe at a total pressure of 2.8 atm up to a total pressure of 10 atm. It is evident that the projected activity for our PPh 3 -Rh/SiO 2 catalyst is similar to those reported by Ding and coworkers.…”

Section: Catalytic Activity Of Pph 3 -Rh/siomentioning

confidence: 99%

“…Sulfur promotion enhances the rate of propene hydroformylation relative to the rate of propene hydrogenation, particularly at high pressure, but the selectivity to butanal is less than *30% at 10 atm. More recently, Ding and coworkers [7][8][9][10][11][12] have demonstrated that high activity, near 100% selectivity, and good stability for the hydroformylation of propene to butanal can be achieved with PPh 3 -modified Rh/SiO 2 . Characterization of these catalysts by 1 H, 29 Si, 31 P, and 17 O MAS NMR, suggests that the active species consist of Rh ?…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Gas-Phase Hydroformylation of Propene over Silica-Supported PPh3-Modified Rhodium Catalysts

et al. 2011

View full text Add to dashboard Cite

Heterogeneous rhodium catalysts supported on SiO 2 were modified with PPh 3 for the gas-phase hydroformylation of propene to produce n-and isobutanal. High selectivity to aldehydes was achieved, with no propane or alcohols formed. Investigation of the effects of reaction temperature, reactant partial pressures, total pressure, and PPh 3 /Rh ratio suggested that the supported catalyst behaved similarly to the homogeneous catalyst. In particular, the supported catalyst showed similar activation energies and partial and total pressure dependences of the reaction rates to those observed in homogeneous, liquidphase reactions. The first order dependence of the hydroformylation rate on the partial pressures of propene, CO, and H 2 individually led to a cubic dependence of butanal formation on total pressure for equimolar reactant mixtures. High regioselectivity with a typical n/i ratio of 14 was achieved.

show abstract

Section: Methodsmentioning

confidence: 99%

“…Also shown are the results for SiO 2 -and SBA-15-supported solutions of HRh(CO)(PPh 3 ) 3 in PPh 3 [8,11]. In all cases, except where sulfoxantphos was used, the PPh 3 /Rh ratio was 15.…”

Section: Catalytic Activity Of Pph 3 -Rh/siomentioning

confidence: 99%

Section: Catalytic Activity Of Pph 3 -Rh/siomentioning

confidence: 99%

Section: Catalytic Activity Of Pph 3 -Rh/siomentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Gas-Phase Hydroformylation of Propene over Silica-Supported PPh3-Modified Rhodium Catalysts

et al. 2011

View full text Add to dashboard Cite

show abstract

ligand‐modified catalysts

Cornils¹

2020

Catalysis From a to Z

View full text Add to dashboard Cite

Heterogeneous Enantioselective Hydrogenation of Aromatic Ketones Catalyzed by Cinchona‐ and Phosphine‐Modified Iridium Catalysts

Yang

et al. 2008

Angewandte Chemie

View full text Add to dashboard Cite

Dedicated to the Catalysis Society of Japan on the occasion of the 50th anniversary Heterogeneous catalytic systems for asymmetric reactions are fascinating because of their potential in synthetic applications.[1] However, because of the high substrate specificity of these catalysts, the complexity of the task at hand, and the difficulties in understanding and designing the catalytic reactions, there have been just three established systems reported.[1a] One system identified for asymmetric hydrogenation is the cinchona-modified Pt/Al 2 O 3 for asymmetric hydrogenation of a-keto esters, which was developed by Orito et al. in 1979. [2] Baiker et al. successfully used this catalyst in the asymmetric hydrogenation of activated aromatic ketones.[3] However, when considering the asymmetric hydrogenation of simple aromatic ketones and derivatives, which are among the most fundamental subjects in modern synthetic chemistry, few successful heterogeneous catalytic examples are reported.Chiral modifiers are the origin of the enantioselectivity in most heterogeneous catalytic reactions, and natural cinchona alkaloids and their derivatives have been widely used as versatile chiral catalysts, ligands, column packing, and chiral shift reagents.[4] Two of the three most well-known heterogeneous catalytic systems in asymmetric reactions are based on natural cinchona alkaloids and their derivatives as the chiral modifiers. [2,5] Stabilizers, which are widely used in preparing nanometal catalysts, including amines, [6] phosphines, [7] and thiols, [8] have been gradually introduced into supported catalysts in recent years. We previously reported polyvinylpyrrolidone (PVP) and cinchona-stabilized Rh in the asymmetric hydrogenation of a-keto esters, in which moderate to good enantioselectivities were obtained.[9] Meanwhile, little attention has been paid to the preparation of supported metal catalysts stabilized by phosphines. Reported herein is a Ph 3 Pstabilized Ir/SiO 2 catalyst system modified by a chiral diamine, derived from cinchona alkaloids, for the asymmetric hydrogenation of simple aromatic ketones and their derivatives; the results are compared to known homogeneous catalysts.[10] To the best of our knowledge, this is the first report of the asymmetric hydrogenation of simple aromatic ketones with a greater than 95 % ee by using a new heterogeneous catalyst. This report is also the first successful example of the asymmetric hydrogenation of simple aromatic ketones employing Ir and H 2 .The high-resolution transmission electron microscopy (HRTEM) picture ( Figure 1 in the Supporting Information) of 3 %Ir/SiO 2 /2tpp (tpp = triphenylphosphine) showed that Ir is highly dispersed on the SiO 2 as an amorphous agglomerate. The X-ray photoelectron spectroscopy (XPS) analysis indicated that the metal component is present in a reduced state (Ir 4f 7/2 core level centered at 61.6 eV) compared to Ir 0 (Ir 4f 7/2 core level centered at 60.8 eV), [11] and the binding energy (103.5 eV) of Si 2p is similar to the expected value (103.4 ...

show abstract

Ligand modified real heterogeneous catalysts for fixed-bed hydroformylation of propylene

Cited by 53 publications

References 30 publications

Gas-Phase Hydroformylation of Propene over Silica-Supported PPh3-Modified Rhodium Catalysts

Gas-Phase Hydroformylation of Propene over Silica-Supported PPh3-Modified Rhodium Catalysts

ligand‐modified catalysts

Heterogeneous Enantioselective Hydrogenation of Aromatic Ketones Catalyzed by Cinchona‐ and Phosphine‐Modified Iridium Catalysts

Contact Info

Product

Resources

About