volume 144 issue 10 pages 1717-1727

Kinetics and Mechanisms of Homogeneous Catalytic Reactions. Part 12. Hydroalcoxycarbonylation of 1-Hexene Using Palladium/Triphenylphosphine Systems as Catalyst Precursors

Publication typeJournal Article
Publication date2014-08-23
scimago Q2
wos Q3
SJR0.539
CiteScore4.9
Impact factor2.4
ISSN1011372X, 1572879X
General Chemistry
Catalysis
Abstract
Systems prepared in situ by addition of n equivalents of triphenylphosphine to palladium dichloride in the presence of m equivalents of para-toluenesulfonic acid (TSA), PdCl2/nPPh3/mTSA (n and m varying between 2 and 10), were used as precatalysts for the olefin carbonylation (1-hexene, cyclohexene and styrene) with alcohols (MeOH, EtOH, n-PrOH and i-PrOH) to generate the corresponding esters (hydroalcoxycarbonylation), under mild reaction conditions. For 1-hexene carbonylation in presence of methanol (1-hexene hydromethoxycarbonylation), the most active system was PdCl2/6PPh3/5TSA at P(CO) = 50 atm and T = 125 °C, which was also active for the hydromethoxycarbonylation of other olefins (1-hexene > styrene > cyclohexene). This system was regioselective towards the linear product for 1-hexene and towards the branched product for styrene. A kinetic study of 1-hexene hydromethoxycarbonylation catalyzed by PdCl2/6PPh3/5TSA showed that the initial reaction rate (r o) was first order on Pd and MeOH concentrations and fractional order with respect to CO concentration; for olefin concentration was found a saturation curve. These kinetic results, together with coordination chemistry and computational DFT studies, allow us to propose a catalytic cycle involving species of the type [Pd(H)(L)(PPh3)2]+n (L = Cl, n = 0; L = CO, MeOH, olefin and PPh3, n = 1) as the catalytically active species and three sequential reactions: (1) olefin insertion into the Pd–H bond to yield Pd–alkyl species, (2) CO insertion into the Pd–C bond to generate Pd–acyl intermediates, and (3) the methanolysis of Pd–acyl species to produce the corresponding methyl esters, regenerate the active species and restart the cycle; the last reaction is considered the rate-determining step (rds) of the mechanism. Systems prepared in situ by addition of triphenylphosphine to palladium dichloride in the presence of para-toluenesulfonic acid (TSA), PdCl2/nPPh3/mTSA were used as precatalysts for the olefin carbonylation with alcohols (MeOH, EtOH, n-PrOH and i-PrOH) to generate the corresponding esters (hydroalcoxycarbonylation), under mild reaction conditions. For 1-hexene hydromethoxycarbonylation, the most active system was PdCl2/6PPh3/5TSA at P(CO) = 50 atm and T = 125 ºC. Kinetic, coordination chemistry and computational DFT studies, allow us to propose a catalytic cycle involving species of the type [Pd(H)(L)(PPh3)2]+n (L = Cl, n = 0; L = CO, MeOH, olefin, n = 1) or [Pd(H)(PPh3)3]+ as the catalytically active species.
Found 
Found 

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Rosales M. et al. Kinetics and Mechanisms of Homogeneous Catalytic Reactions. Part 12. Hydroalcoxycarbonylation of 1-Hexene Using Palladium/Triphenylphosphine Systems as Catalyst Precursors // Catalysis Letters. 2014. Vol. 144. No. 10. pp. 1717-1727.
GOST all authors (up to 50) Copy
Rosales M., Pacheco I., Medina J., Fernandez J., González Á., Izquierdo R., Melean L. G., Baricelli P. J. Kinetics and Mechanisms of Homogeneous Catalytic Reactions. Part 12. Hydroalcoxycarbonylation of 1-Hexene Using Palladium/Triphenylphosphine Systems as Catalyst Precursors // Catalysis Letters. 2014. Vol. 144. No. 10. pp. 1717-1727.
RIS |
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RIS Copy
TY - JOUR
DO - 10.1007/s10562-014-1335-0
UR - https://doi.org/10.1007/s10562-014-1335-0
TI - Kinetics and Mechanisms of Homogeneous Catalytic Reactions. Part 12. Hydroalcoxycarbonylation of 1-Hexene Using Palladium/Triphenylphosphine Systems as Catalyst Precursors
T2 - Catalysis Letters
AU - Rosales, Merlin
AU - Pacheco, Inés
AU - Medina, Jairo
AU - Fernandez, Juan
AU - González, Ángel
AU - Izquierdo, Rodolfo
AU - Melean, Luis G
AU - Baricelli, Pablo J.
PY - 2014
DA - 2014/08/23
PB - Springer Nature
SP - 1717-1727
IS - 10
VL - 144
SN - 1011-372X
SN - 1572-879X
ER -
BibTex |
Cite this
BibTex (up to 50 authors) Copy
@article{2014_Rosales,
author = {Merlin Rosales and Inés Pacheco and Jairo Medina and Juan Fernandez and Ángel González and Rodolfo Izquierdo and Luis G Melean and Pablo J. Baricelli},
title = {Kinetics and Mechanisms of Homogeneous Catalytic Reactions. Part 12. Hydroalcoxycarbonylation of 1-Hexene Using Palladium/Triphenylphosphine Systems as Catalyst Precursors},
journal = {Catalysis Letters},
year = {2014},
volume = {144},
publisher = {Springer Nature},
month = {aug},
url = {https://doi.org/10.1007/s10562-014-1335-0},
number = {10},
pages = {1717--1727},
doi = {10.1007/s10562-014-1335-0}
}
MLA
Cite this
MLA Copy
Rosales, Merlin, et al. “Kinetics and Mechanisms of Homogeneous Catalytic Reactions. Part 12. Hydroalcoxycarbonylation of 1-Hexene Using Palladium/Triphenylphosphine Systems as Catalyst Precursors.” Catalysis Letters, vol. 144, no. 10, Aug. 2014, pp. 1717-1727. https://doi.org/10.1007/s10562-014-1335-0.