Highly efficient catalytic system for the formation of dialdehydes from dicyclopentadiene hydroformylation

Luo, Rong; Liang, Haoran; Zheng, Xueli; Fu, Haiyan; Li, Ruixiang; Chen, Hua

doi:10.1016/j.catcom.2014.02.025

Cited by 24 publications

(6 citation statements)

References 21 publications

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“…Modifying Rh-loaded mesoporous silica support with a cobalt catalyst resulted in MFTD and DFTD yields of 87% and 88.7% [12], respectively. Chen et al reported high conversion (99.9%) and good selectivity (95.0%) to dialdehydes in the presence of Rh/mixed monodentate and bidentate phosphorus ligand complexes under optimized reaction conditions [13]. We recently showed that MFTD and DFTD yields of 97% and 84%, respectively, could be achieved over a cobalt-modified iron oxide-Rh/Fe 3 O 4 catalyst [14].…”

Section: Introductionmentioning

confidence: 94%

Dicyclopentadiene Hydroformylation to Value-Added Fine Chemicals over Magnetically Separable Fe3O4-Supported Co-Rh Bimetallic Catalysts: Effects of Cobalt Loading

Gao

et al. 2017

Catalysts

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Six Co-Rh/Fe 3 O 4 catalysts with different cobalt loadings were prepared by the co-precipitation of RhCl 3 , Co(NO 3 ) 2 , and Fe(NO 3 ) 3 using Na 2 CO 3 as the precipitant. These catalysts were tested for dicyclopentadiene (DCPD) hydroformylation to monoformyltricyclodecenes (MFTD) and diformyltricyclodecanes (DFTD). The results showed that the MFTD formation rate increased with increasing cobalt loading, whereas the DFTD formation rate initially increased and then decreased when the cobalt loading was greater than twice that of Rh. The DFTD selectivity was only 21.3% when monometallic Rh/Fe 3 O 4 was used as the catalyst. In contrast, the selectivity was 90.6% at a similar DCPD conversion when the bimetallic 4Co-2Rh/Fe 3 O 4 catalyst was employed. These catalysts were characterized by temperature-programmed reduction (TPR), temperature-programmed desorption (TPD), and thermogravimetric and differential thermal analyses (TG-DTA). The results obtained by these complimentary characterization techniques indicated that adding cobalt to the Rh/Fe 3 O 4 catalyst enhanced the Rh reducibility and dispersion; the Rh reducibility was easily altered, and increasing the cobalt loading improved the Rh dispersion. It was concluded that the enhanced catalytic performance with increasing cobalt loading might be due to the formation of a more reactive Rh species with a different Rh-phosphine interaction strength on the catalyst surface.

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Section: Introductionmentioning

confidence: 94%

Dicyclopentadiene Hydroformylation to Value-Added Fine Chemicals over Magnetically Separable Fe3O4-Supported Co-Rh Bimetallic Catalysts: Effects of Cobalt Loading

Gao

et al. 2017

Catalysts

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“…It is reported that the addition of phosphine ligand to the hydroformylation reaction system can exert a significant promotion effect on the catalysis thus lowering the requirement for high reaction temperature and pressure [19][20][21][22] .…”

Section: Recentlymentioning

confidence: 99%

Tandem hydroformylation and hydrogenation of dicyclopentadiene by Co₃O₄ supported gold nanoparticles

Qing

Gao

et al. 2015

Catal. Sci. Technol.

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A co-precipitation method was used to prepare a series of Co 3 O 4 supported gold nanoparticles (Au/Co 3 O 4 ), which were subsequently evaluated on their performances for "one-pot" synthesis of tricyclodecanedimethylol (TDDMO) from dicyclopentadiene (DCPD). Characterization methods including FTIR, XPS and TG-DTA were performed on the Au/Co 3 O 4 catalyst during the course of reaction to reveal that three distinct stages of catalysis occurred while the catalyst possessed different physiochemical properties. "One-pot" synthesis of TDDMO was successfully realized with selectivity over 90% under relatively mild reaction conditions of 140-150 o C reaction temperature and 7-9 MPa pressure. Experimental data suggested that the catalytically active species might be a Co(CO) x (PPh) y complex where the presence of gold can assist the in-situ reduction of Co 3 O 4 to metallic cobalt under reaction conditions, thereby increasing the number of active sites. Another role of Au was proposed as facilitating hydrogenation of in-situ formed intermediate aldehyde, diformyltricyclodecanes (DFTD), to produce the final product TDDMO.

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“…[22] Styrene, a-methylstyrene, and dicyclopentadiene have also been transformed into aldehydes with Rh systemst hat contain pyrrolylphosphines. [23][24][25][26] For example, the conversion of a-methylstyrene increased from 42.6 %f or PPh 3 to 97.2 %i fP(Pyr) 3 was used. [25] Notably,i n1 -hexene hydroformylation with different Rh I precursors and pyrrolylphosphines, [17][18][19][20][21] the yield of aldehydes and selectivity to n-heptanal are significantly higher than that with PPh 3 .…”

Section: Introductionmentioning

confidence: 99%

“…[27][28][29] The best results in ethene hydroformylation have been obtainedf or Rh(acac)(CO) 2 /PPyr 3 (acac = acetylacetonate). [26] Ag ood regioselectivity and high activity have been achieved in the Rh-catalyzed hydroformylation of 1-octene with bidentate N-pyrrolylphosphine. [30] Rh complexes with tripyrrolylphosphine, [RhCl(cod)(PPyr 3 )] (cod = cyclooctadiene), [HRhCO(PPyr 3 ) 3 ], and HRh(PPyr 3 ) 4 have also been appliedi nt he hydrogenation of organonitriles, [31] cyclic olefins, and aromatics.…”

Section: Introductionmentioning

confidence: 99%

Rhodium Pyrrolylphosphine Complexes as Highly Active and Selective Catalysts for Propene Hydroformylation: The Effect of Water and Aldehyde on the Reaction Regioselectivity

2017

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The hydroformylation of propene catalyzed by Rh(acac)(CO)2 (acac=acetylacetonate) with a 13‐fold excess of N‐pyrrolylphosphine ligands PPyr3, PPh2Pyr, or PPh(Pyr)2 (Pyr=NC4H4) was investigated under a pressure of 15 bar (propene/H2/CO=5:5:5) at 80 °C. The N‐pyrrolylphosphine ligands facilitated an excellent regioselectivity towards n‐butanal aldehyde, significantly better than PPh3 and PCy3 under the same conditions. In the presence of the strongest π‐acceptor, PPyr3, the linear‐to‐branched aldehyde (l/b) ratio was 8.6, which increased to 27.1 if water was added to the system. The application of a pure aldehyde as a solvent instead of toluene caused a significant increase in the aldehyde yield but with a decreased l/b ratio (2.9–7.6). The regioselectivity parameter l/b increased to 19.3 after the introduction of water as a cosolvent.

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Highly efficient catalytic system for the formation of dialdehydes from dicyclopentadiene hydroformylation

Cited by 24 publications

References 21 publications

Dicyclopentadiene Hydroformylation to Value-Added Fine Chemicals over Magnetically Separable Fe3O4-Supported Co-Rh Bimetallic Catalysts: Effects of Cobalt Loading

Dicyclopentadiene Hydroformylation to Value-Added Fine Chemicals over Magnetically Separable Fe3O4-Supported Co-Rh Bimetallic Catalysts: Effects of Cobalt Loading

Tandem hydroformylation and hydrogenation of dicyclopentadiene by Co₃O₄ supported gold nanoparticles

Rhodium Pyrrolylphosphine Complexes as Highly Active and Selective Catalysts for Propene Hydroformylation: The Effect of Water and Aldehyde on the Reaction Regioselectivity

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Highly efficient catalytic system for the formation of dialdehydes from dicyclopentadiene hydroformylation

Cited by 24 publications

References 21 publications

Dicyclopentadiene Hydroformylation to Value-Added Fine Chemicals over Magnetically Separable Fe3O4-Supported Co-Rh Bimetallic Catalysts: Effects of Cobalt Loading

Dicyclopentadiene Hydroformylation to Value-Added Fine Chemicals over Magnetically Separable Fe3O4-Supported Co-Rh Bimetallic Catalysts: Effects of Cobalt Loading

Tandem hydroformylation and hydrogenation of dicyclopentadiene by Co3O4 supported gold nanoparticles

Rhodium Pyrrolylphosphine Complexes as Highly Active and Selective Catalysts for Propene Hydroformylation: The Effect of Water and Aldehyde on the Reaction Regioselectivity

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Tandem hydroformylation and hydrogenation of dicyclopentadiene by Co₃O₄ supported gold nanoparticles