Influence of the lanthanide(III) ion in {[Cu3Ln2(oda)6(H2O)6]•nH2O}n (LnIII: La, Gd, Yb) catalysts on the heterogeneous oxidation of olefins

P. Cancino, V. Paredes-García, C. Aliaga, P. Aguirre, D. Aravena, E. Spodine

Resultado de la investigación: Article

6 Citas (Scopus)

Resumen

{[Cu3Ln2(oda)6(H2O)6]•nH2O}n (LnIII: La, Gd, Yb; odaH2: oxydiacetic acid) are reported as reusable heterogeneous catalysts in the oxidation of olefins. An influence of the LnIII ion on the catalytic performance of the series is observed, where the YbIII based framework presents a larger activity. The mentioned heteronuclear species are catalytically more active than the corresponding homonuclear catalyst {[Cu(oda)2]•0.5H2O}n. The use of t-butyl hydroperoxide (TBHP) as an oxidant gave conversions between 73-63% for styrene oxidation and between 57-48% for cyclohexene in dichloroethane/water (DCE/H2O). In four cycles, the loss of catalytic activity was less than 10%. Experimental data permit the consideration of the redox active CuII centres as the initiators of radical species generated from TBHP, which are responsible for the oxidation process of the studied olefins. Electron paramagnetic resonance (EPR) spectra of the reaction solutions, obtained in the presence of the spin trap PBN (N-tert-butyl-α-phenylnitrone), corroborate radical species formation during the oxidation process. DFT calculations support an electronic influence of the LnIII ions on the reactivity of the CuII centre, associated with changes in the stabilization of the empty CuII 3dx2 -y2 orbital, affecting the reduction of CuII with TBHP to CuI. Model calculations employing several density functionals support a higher electron affinity in the CuGdMOF system in comparison to CuLaMOF. In this way, electronic structure calculations agree with the interesting observed trend of the influence of the secondary metal centre (LnIII ions) on the properties of the active centre (CuII).

Idioma originalEnglish
Páginas (desde-hasta)231-242
Número de páginas12
PublicaciónCatalysis Science and Technology
Volumen7
N.º1
DOI
EstadoPublished - 2017

Huella dactilar

Lanthanoid Series Elements
Alkenes
Rare earth elements
tert-Butylhydroperoxide
Olefins
Ions
Oxidation
Catalysts
Ethylene Dichlorides
Electron affinity
Styrene
Oxidants
Discrete Fourier transforms
Electronic structure
Paramagnetic resonance
Catalyst activity
Stabilization
Metals
Acids
Water

ASJC Scopus subject areas

  • Catalysis

Citar esto

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title = "Influence of the lanthanide(III) ion in {[Cu3Ln2(oda)6(H2O)6]•nH2O}n (LnIII: La, Gd, Yb) catalysts on the heterogeneous oxidation of olefins",
abstract = "{[Cu3Ln2(oda)6(H2O)6]•nH2O}n (LnIII: La, Gd, Yb; odaH2: oxydiacetic acid) are reported as reusable heterogeneous catalysts in the oxidation of olefins. An influence of the LnIII ion on the catalytic performance of the series is observed, where the YbIII based framework presents a larger activity. The mentioned heteronuclear species are catalytically more active than the corresponding homonuclear catalyst {[Cu(oda)2]•0.5H2O}n. The use of t-butyl hydroperoxide (TBHP) as an oxidant gave conversions between 73-63{\%} for styrene oxidation and between 57-48{\%} for cyclohexene in dichloroethane/water (DCE/H2O). In four cycles, the loss of catalytic activity was less than 10{\%}. Experimental data permit the consideration of the redox active CuII centres as the initiators of radical species generated from TBHP, which are responsible for the oxidation process of the studied olefins. Electron paramagnetic resonance (EPR) spectra of the reaction solutions, obtained in the presence of the spin trap PBN (N-tert-butyl-α-phenylnitrone), corroborate radical species formation during the oxidation process. DFT calculations support an electronic influence of the LnIII ions on the reactivity of the CuII centre, associated with changes in the stabilization of the empty CuII 3dx2 -y2 orbital, affecting the reduction of CuII with TBHP to CuI. Model calculations employing several density functionals support a higher electron affinity in the CuGdMOF system in comparison to CuLaMOF. In this way, electronic structure calculations agree with the interesting observed trend of the influence of the secondary metal centre (LnIII ions) on the properties of the active centre (CuII).",
author = "P. Cancino and V. Paredes-Garc{\'i}a and C. Aliaga and P. Aguirre and D. Aravena and E. Spodine",
year = "2017",
doi = "10.1039/c6cy02115h",
language = "English",
volume = "7",
pages = "231--242",
journal = "Catalysis Science and Technology",
issn = "2044-4753",
publisher = "Royal Society of Chemistry",
number = "1",

}

Influence of the lanthanide(III) ion in {[Cu3Ln2(oda)6(H2O)6]•nH2O}n (LnIII : La, Gd, Yb) catalysts on the heterogeneous oxidation of olefins. / Cancino, P.; Paredes-García, V.; Aliaga, C.; Aguirre, P.; Aravena, D.; Spodine, E.

En: Catalysis Science and Technology, Vol. 7, N.º 1, 2017, p. 231-242.

Resultado de la investigación: Article

TY - JOUR

T1 - Influence of the lanthanide(III) ion in {[Cu3Ln2(oda)6(H2O)6]•nH2O}n (LnIII

T2 - La, Gd, Yb) catalysts on the heterogeneous oxidation of olefins

AU - Cancino, P.

AU - Paredes-García, V.

AU - Aliaga, C.

AU - Aguirre, P.

AU - Aravena, D.

AU - Spodine, E.

PY - 2017

Y1 - 2017

N2 - {[Cu3Ln2(oda)6(H2O)6]•nH2O}n (LnIII: La, Gd, Yb; odaH2: oxydiacetic acid) are reported as reusable heterogeneous catalysts in the oxidation of olefins. An influence of the LnIII ion on the catalytic performance of the series is observed, where the YbIII based framework presents a larger activity. The mentioned heteronuclear species are catalytically more active than the corresponding homonuclear catalyst {[Cu(oda)2]•0.5H2O}n. The use of t-butyl hydroperoxide (TBHP) as an oxidant gave conversions between 73-63% for styrene oxidation and between 57-48% for cyclohexene in dichloroethane/water (DCE/H2O). In four cycles, the loss of catalytic activity was less than 10%. Experimental data permit the consideration of the redox active CuII centres as the initiators of radical species generated from TBHP, which are responsible for the oxidation process of the studied olefins. Electron paramagnetic resonance (EPR) spectra of the reaction solutions, obtained in the presence of the spin trap PBN (N-tert-butyl-α-phenylnitrone), corroborate radical species formation during the oxidation process. DFT calculations support an electronic influence of the LnIII ions on the reactivity of the CuII centre, associated with changes in the stabilization of the empty CuII 3dx2 -y2 orbital, affecting the reduction of CuII with TBHP to CuI. Model calculations employing several density functionals support a higher electron affinity in the CuGdMOF system in comparison to CuLaMOF. In this way, electronic structure calculations agree with the interesting observed trend of the influence of the secondary metal centre (LnIII ions) on the properties of the active centre (CuII).

AB - {[Cu3Ln2(oda)6(H2O)6]•nH2O}n (LnIII: La, Gd, Yb; odaH2: oxydiacetic acid) are reported as reusable heterogeneous catalysts in the oxidation of olefins. An influence of the LnIII ion on the catalytic performance of the series is observed, where the YbIII based framework presents a larger activity. The mentioned heteronuclear species are catalytically more active than the corresponding homonuclear catalyst {[Cu(oda)2]•0.5H2O}n. The use of t-butyl hydroperoxide (TBHP) as an oxidant gave conversions between 73-63% for styrene oxidation and between 57-48% for cyclohexene in dichloroethane/water (DCE/H2O). In four cycles, the loss of catalytic activity was less than 10%. Experimental data permit the consideration of the redox active CuII centres as the initiators of radical species generated from TBHP, which are responsible for the oxidation process of the studied olefins. Electron paramagnetic resonance (EPR) spectra of the reaction solutions, obtained in the presence of the spin trap PBN (N-tert-butyl-α-phenylnitrone), corroborate radical species formation during the oxidation process. DFT calculations support an electronic influence of the LnIII ions on the reactivity of the CuII centre, associated with changes in the stabilization of the empty CuII 3dx2 -y2 orbital, affecting the reduction of CuII with TBHP to CuI. Model calculations employing several density functionals support a higher electron affinity in the CuGdMOF system in comparison to CuLaMOF. In this way, electronic structure calculations agree with the interesting observed trend of the influence of the secondary metal centre (LnIII ions) on the properties of the active centre (CuII).

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U2 - 10.1039/c6cy02115h

DO - 10.1039/c6cy02115h

M3 - Article

AN - SCOPUS:85017348896

VL - 7

SP - 231

EP - 242

JO - Catalysis Science and Technology

JF - Catalysis Science and Technology

SN - 2044-4753

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