Co-catalysis over a tri-functional ligand modified Pd-catalyst for hydroxycarbonylation of terminal alkynes towards α,β-unsaturated carboxylic acids

Yang, Da; Huan, Long; Liu, Lei; Guo, Wu; Lu, Yong; Liu, Ye

doi:10.1039/c9gc01887e

Cited by 27 publications

(8 citation statements)

References 41 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…As shown in Figure 8, two obvious broad peaks at around 2170 and 2100 cm −1 assigned to the gaseous CO were clearly observed. When the temperature increased from 25 to 110 °C, an absorption peak at around 1941 cm −1 attributed to the Pd II -H species 54 appeared and became stronger gradually. With the emergence of the peak at 1941 cm −1 , a characteristic peak at around 1700 cm −1 assigned to the absorption of the carbonyl group in phenylpropionic acid was observed.…”

Section: Acs Sustainablementioning

confidence: 99%

Hydrocarboxylation of Olefins Catalyzed by Polyoxometalate-Anchored Palladium Single-Atom Catalysts

Jiang

Wei

et al. 2022

ACS Sustainable Chem. Eng.

View full text Add to dashboard Cite

Herein, the Keggin-type polyoxometalate (POM)a n c h o r e d p a l l a d i u m s i n g l e -a t o m c a t a l y s t s [ ( n -C 4 H 9 ) 4 N] 6 [SiW 11 O 39 Pd] and [(n-C 4 H 9 ) 4 N] 5 [PW 11 O 39 Pd] were constructed and employed in the olefin hydrocarboxylation reaction under two-phase conditions. Both the conversion of styrene and the yield of the carboxylic acids can reach as high as 95% at 110 °C. The characterization by high-angle annular darkfield scanning transmission electron microscopy (HAADF-STEM), electrospray ionization mass spectrometry (ESI-MS), and in situ Fourier-transform infrared (FT-IR) spectra of CO adsorption indicated the incorporation of the isolated Pd atom into the POM structure. The POM-anchored Pd catalysts can be directly stored under an ambient atmosphere and easily recovered in consecutive catalytic recycling. Tetrabutylammonium bromide (TBAB) played a crucial role in stabilizing/dispersing the Pd catalyst. Moreover, the catalytic systems showed a unique "pseudo-liquid-phase" behavior and the reactants were absorbed into the flexible POM anions. The catalysts exhibited a wide substrate suitability and have been applied under phosphine ligand-free conditions. The catalytic mechanism studies involving D 2 O showed that the hydrocarboxylation reaction proceeds through the "Pd−H" pathway.

show abstract

Section: Acs Sustainablementioning

confidence: 99%

Hydrocarboxylation of Olefins Catalyzed by Polyoxometalate-Anchored Palladium Single-Atom Catalysts

Jiang

Wei

et al. 2022

ACS Sustainable Chem. Eng.

View full text Add to dashboard Cite

show abstract

“…After the addition of two equivalent of PTSA, this peak disappeared completely and new peaks located at 35.39 to −8.64 ppm appeared, which indicated the structure of the palladium complex and microenvironment of the solution have changed significantly. It has been proved that the Pd(II)–hydride complexes were the key active Pd species in the alkoxycarbonylation reaction; ,, we then further conducted the reaction of Pd(OAc) 2 and DPL20 in methanol at 100 °C under a N 2 atmosphere and recorded the 1 H NMR spectrum of this reaction mixture. The Pd(II)–hydride species was observed in the presence of PTSA, and the resonances of Pd–H were recorded at about δ 1 H −8.36 ppm (doublet of doublet with 2 J PH trans = 189.3 Hz and 2 J PH cis = 9.4 Hz) (Figure S2b).…”

Section: Resultsmentioning

confidence: 99%

Sustainable Production of Emerging Diesel Additive from Butene by Palladium-Catalyzed Alkoxycarbonylation

Dong

Fang

et al. 2023

ACS Sustainable Chem. Eng.

View full text Add to dashboard Cite

Pentanoic esters are a new class of biofuels (additives) and are typically produced from biomass-derived levulinic acid/esters via hydrogenation-cyclization/ring-opening/ hydrogenation three-step transformations. Here, a one-step and atom-economic alkoxycarbonylation route is developed to produce pentanoic esters from widely available 1-butene. Based on the screening of 21 monophosphine and 26 diphosphine ligands, a Pd/ diphosphine ligand (bis(2-diphenylphosphinophenyl) ether, DPEphos) system gives 91% yield of linear and branched ethyl pentanoate (78/22 ratio) with a turnover number (TON) up to 26100 and demonstrates outstanding recycle potential. The apparent activation energy (E a ) of 1-butene alkoxycarbonylation in the presence of this catalytic system was estimated to be 89.4 kJ/mol via kinetic measurements. More importantly, homogeneously blending 10 vol % of the resultant esters in pure diesel can improve the low-temperature fluidity and pumpability of diesel and decrease the emission of exhaust pollutants of diesel without affecting the power performance of diesel engines. Compared with pure diesel, the CO, NO x , HC, and soot emission of blend diesel at 2500 rpm are reduced by 28%, 9%, 6%, and 42%, respectively. This work provides a promising route to produce high-performance fuel additive and simultaneously broadens the comprehensive utilization of C4 olefin.

show abstract

“…Moreover, PdÀ H species (1932 cm À 1 ) were generated, which may be caused by the desorption of products. [21] The peak at 2164 cm À 1 can be assigned to the linear CO adsorption species on Pd 2 + , obviously stronger than that in Figure S12b with only CO, indicating that the addition of air maintains the valence state of Pd 2 + . [17c] The above-mentioned peaks on Pd 1 /PIPs all emerged on Pd 1 À Ru 1 /PIPs (Figure 3c).…”

Section: Methodsmentioning

confidence: 97%

Palladium and Ruthenium Dual‐Single‐Atom Sites on Porous Ionic Polymers for Acetylene Dialkoxycarbonylation: Synergetic Effects Stabilize the Active Site and Increase CO Adsorption

Wang

Qiao

et al. 2023

Angew Chem Int Ed

View full text Add to dashboard Cite

Heterogeneous single‐metal‐site catalysts usually suffer from poor stability, thereby limiting industrial applications. Dual Pd1−Ru1 single‐atom‐sites supported on porous ionic polymers (Pd1−Ru1/PIPs) were constructed using a wetness impregnation method. The two isolated metal species in the form of a binuclear complex were immobilized on the cationic framework of PIPs through ionic bonds. Compared to the single Pd‐ or Ru‐site catalyst, the dual single‐atom system exhibits higher activity with 98 % acetylene conversion and near 100 % selectivity to dialkoxycarbonylation products, as well as better cycling stability for ten cycles without obvious decay. Based on DFT calculations, it was found that the single‐Ru site exhibited a strong CO adsorption energy of −1.6 eV, leading to an increase in the local CO concentration of the catalyst. Notably, the Pd1−Ru1/PIPs catalyst had a much lower energy barrier of 2.49 eV compared to 3.87 eV of Pd1/PIPs for the rate‐determining step. The synergetic effect between neighboring single sites Pd1 and Ru1 not only enhanced the overall activity, but also stabilized PdII active sites. The discovery of synergetic effects between single sites can deepen our understanding of single‐site catalysts at the molecular level.

show abstract

Co-catalysis over a tri-functional ligand modified Pd-catalyst for hydroxycarbonylation of terminal alkynes towards α,β-unsaturated carboxylic acids

Abstract: An amphiphilic tri-functional ligand (L1) containing a phosphonium cation, a phosphino-fragment and a hydrophilic sulfonate anion enabled Pd(OAc)2 to co-catalyze hydroxycarbonylation of terminal alkynes towards α,β-unsaturated carboxylic acids.

Cited by 27 publications

References 41 publications

Hydrocarboxylation of Olefins Catalyzed by Polyoxometalate-Anchored Palladium Single-Atom Catalysts

Hydrocarboxylation of Olefins Catalyzed by Polyoxometalate-Anchored Palladium Single-Atom Catalysts

Sustainable Production of Emerging Diesel Additive from Butene by Palladium-Catalyzed Alkoxycarbonylation

Palladium and Ruthenium Dual‐Single‐Atom Sites on Porous Ionic Polymers for Acetylene Dialkoxycarbonylation: Synergetic Effects Stabilize the Active Site and Increase CO Adsorption

Contact Info

Product

Resources

About