Enantioselective hydrogenation of 1-phenyl-1,2-propanodione on cinchonidine-modified Rh/MCM-41 catalysts

Cecilia C. Torres, Cristian H. Campos, J. L.G. Fierro, Patricio Reyes, Doris Ruiz

Resultado de la investigación: Article

12 Citas (Scopus)

Resumen

Enantioselective hydrogenation of 1-phenyl-1,2-propanodione (PPD) on Rh/MCM-41 catalysts was studied. The catalysts were prepared using Rh(acac) 3 as a metal precursor and metal loadings that ranged from 0.5 to 1.5 wt%. The samples were characterised by nitrogen adsorption-desorption isotherms at 77 K using ICP-MS, XRD, TEM, XRD and XPS. The reaction was performed at 298 K, and 0.01 mol L-1 of PPD and cinchonidine (CD) was used as chiral modifier. The effect of the modifier concentration on the enantioselectivity (ee) and the conversion level in the hydrogenation reaction shows a relationship between the activity and ee as well as the CD concentration. The volcano-type curve observed for each catalyst suggests competitive adsorption of the modifier and substrate on the catalyst surface. The metal loading influences both the Rh crystallite size and catalytic behaviour. An increase in the Rh levels was accompanied by a parallel increase in both the crystallite size and number of Rh ensembles with a subsequent enhancement in both the conversion level and ee. The catalyst with the highest metal loading was 1.0 wt% Rh/MCM-41, and it displayed the highest ee among the catalysts studied. Additionally, the effects of hydrogen pressure and solvent nature on the catalytic activity were also studied. Moreover, the H2 pressure also influenced the conversion levels with only a minor effect on the ee values. Considering the solvent effects, we observed non-linear ee dependence with an increasing solvent dielectric constant, which showed a decrease in conversion levels in the order cyclohexane > toluene > tetrahydrofurane > dichloromethane.

Idioma originalEnglish
Páginas (desde-hasta)321-328
Número de páginas8
PublicaciónJournal of Molecular Catalysis A: Chemical
Volumen392
DOI
EstadoPublished - 1 ene 2014

Huella dactilar

Enantioselectivity
Multicarrier modulation
Hydrogenation
hydrogenation
catalysts
Catalysts
Metals
Crystallite size
metals
Adsorption
Volcanoes
adsorption
inductively coupled plasma mass spectrometry
Methylene Chloride
Dichloromethane
Toluene
Cyclohexane
volcanoes
cyclohexane
Isotherms

ASJC Scopus subject areas

  • Catalysis
  • Process Chemistry and Technology
  • Physical and Theoretical Chemistry

Citar esto

Torres, Cecilia C. ; Campos, Cristian H. ; Fierro, J. L.G. ; Reyes, Patricio ; Ruiz, Doris. / Enantioselective hydrogenation of 1-phenyl-1,2-propanodione on cinchonidine-modified Rh/MCM-41 catalysts. En: Journal of Molecular Catalysis A: Chemical. 2014 ; Vol. 392. pp. 321-328.
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title = "Enantioselective hydrogenation of 1-phenyl-1,2-propanodione on cinchonidine-modified Rh/MCM-41 catalysts",
abstract = "Enantioselective hydrogenation of 1-phenyl-1,2-propanodione (PPD) on Rh/MCM-41 catalysts was studied. The catalysts were prepared using Rh(acac) 3 as a metal precursor and metal loadings that ranged from 0.5 to 1.5 wt{\%}. The samples were characterised by nitrogen adsorption-desorption isotherms at 77 K using ICP-MS, XRD, TEM, XRD and XPS. The reaction was performed at 298 K, and 0.01 mol L-1 of PPD and cinchonidine (CD) was used as chiral modifier. The effect of the modifier concentration on the enantioselectivity (ee) and the conversion level in the hydrogenation reaction shows a relationship between the activity and ee as well as the CD concentration. The volcano-type curve observed for each catalyst suggests competitive adsorption of the modifier and substrate on the catalyst surface. The metal loading influences both the Rh crystallite size and catalytic behaviour. An increase in the Rh levels was accompanied by a parallel increase in both the crystallite size and number of Rh ensembles with a subsequent enhancement in both the conversion level and ee. The catalyst with the highest metal loading was 1.0 wt{\%} Rh/MCM-41, and it displayed the highest ee among the catalysts studied. Additionally, the effects of hydrogen pressure and solvent nature on the catalytic activity were also studied. Moreover, the H2 pressure also influenced the conversion levels with only a minor effect on the ee values. Considering the solvent effects, we observed non-linear ee dependence with an increasing solvent dielectric constant, which showed a decrease in conversion levels in the order cyclohexane > toluene > tetrahydrofurane > dichloromethane.",
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Enantioselective hydrogenation of 1-phenyl-1,2-propanodione on cinchonidine-modified Rh/MCM-41 catalysts. / Torres, Cecilia C.; Campos, Cristian H.; Fierro, J. L.G.; Reyes, Patricio; Ruiz, Doris.

En: Journal of Molecular Catalysis A: Chemical, Vol. 392, 01.01.2014, p. 321-328.

Resultado de la investigación: Article

TY - JOUR

T1 - Enantioselective hydrogenation of 1-phenyl-1,2-propanodione on cinchonidine-modified Rh/MCM-41 catalysts

AU - Torres, Cecilia C.

AU - Campos, Cristian H.

AU - Fierro, J. L.G.

AU - Reyes, Patricio

AU - Ruiz, Doris

PY - 2014/1/1

Y1 - 2014/1/1

N2 - Enantioselective hydrogenation of 1-phenyl-1,2-propanodione (PPD) on Rh/MCM-41 catalysts was studied. The catalysts were prepared using Rh(acac) 3 as a metal precursor and metal loadings that ranged from 0.5 to 1.5 wt%. The samples were characterised by nitrogen adsorption-desorption isotherms at 77 K using ICP-MS, XRD, TEM, XRD and XPS. The reaction was performed at 298 K, and 0.01 mol L-1 of PPD and cinchonidine (CD) was used as chiral modifier. The effect of the modifier concentration on the enantioselectivity (ee) and the conversion level in the hydrogenation reaction shows a relationship between the activity and ee as well as the CD concentration. The volcano-type curve observed for each catalyst suggests competitive adsorption of the modifier and substrate on the catalyst surface. The metal loading influences both the Rh crystallite size and catalytic behaviour. An increase in the Rh levels was accompanied by a parallel increase in both the crystallite size and number of Rh ensembles with a subsequent enhancement in both the conversion level and ee. The catalyst with the highest metal loading was 1.0 wt% Rh/MCM-41, and it displayed the highest ee among the catalysts studied. Additionally, the effects of hydrogen pressure and solvent nature on the catalytic activity were also studied. Moreover, the H2 pressure also influenced the conversion levels with only a minor effect on the ee values. Considering the solvent effects, we observed non-linear ee dependence with an increasing solvent dielectric constant, which showed a decrease in conversion levels in the order cyclohexane > toluene > tetrahydrofurane > dichloromethane.

AB - Enantioselective hydrogenation of 1-phenyl-1,2-propanodione (PPD) on Rh/MCM-41 catalysts was studied. The catalysts were prepared using Rh(acac) 3 as a metal precursor and metal loadings that ranged from 0.5 to 1.5 wt%. The samples were characterised by nitrogen adsorption-desorption isotherms at 77 K using ICP-MS, XRD, TEM, XRD and XPS. The reaction was performed at 298 K, and 0.01 mol L-1 of PPD and cinchonidine (CD) was used as chiral modifier. The effect of the modifier concentration on the enantioselectivity (ee) and the conversion level in the hydrogenation reaction shows a relationship between the activity and ee as well as the CD concentration. The volcano-type curve observed for each catalyst suggests competitive adsorption of the modifier and substrate on the catalyst surface. The metal loading influences both the Rh crystallite size and catalytic behaviour. An increase in the Rh levels was accompanied by a parallel increase in both the crystallite size and number of Rh ensembles with a subsequent enhancement in both the conversion level and ee. The catalyst with the highest metal loading was 1.0 wt% Rh/MCM-41, and it displayed the highest ee among the catalysts studied. Additionally, the effects of hydrogen pressure and solvent nature on the catalytic activity were also studied. Moreover, the H2 pressure also influenced the conversion levels with only a minor effect on the ee values. Considering the solvent effects, we observed non-linear ee dependence with an increasing solvent dielectric constant, which showed a decrease in conversion levels in the order cyclohexane > toluene > tetrahydrofurane > dichloromethane.

KW - 1-phenyl-1,2-propanedione

KW - Enantioselectivity

KW - Hydrogenation

KW - Rh catalysts

UR - http://www.scopus.com/inward/record.url?scp=84903202874&partnerID=8YFLogxK

U2 - 10.1016/j.molcata.2014.06.002

DO - 10.1016/j.molcata.2014.06.002

M3 - Article

AN - SCOPUS:84903202874

VL - 392

SP - 321

EP - 328

JO - Journal of Molecular Catalysis A: Chemical

JF - Journal of Molecular Catalysis A: Chemical

SN - 1381-1169

ER -