RT info:eu-repo/semantics/article
T1 An Efficient Microkinetic Modeling Protocol: Start with Only the Dominant Mechanisms, Adjust All Parameters, and Build the Complete Model Incrementally
A1 López-Pérez, José L.
A1 Jaraíz Maldonado, Martín
A1 Rubio García, José Emiliano
A1 Enríquez Giraudo, María Lourdes
A1 Pinacho Gómez, Ruth
A1 Lesarri Gómez, Alberto Eugenio
K1 mechanism
K1 DFT
K1 kinetic
K1 microkinetic
K1 modeling
AB In a recent article (ACS Catal.2018, 8, 11119–11133), a comprehensive catalytic mechanism is proposed to explain the effects of residual water on the reactivity and regioselectivity of tris(pentafluorophenyl)borane catalyst in the ring-opening reaction of 1,2-epoxyoctane by 2-propanol. Using it as a representative example of a common trend followed also by other groups, we show that the heavily under-constrained (loose) kinetic modeling approach employed can lead to several pitfalls and propose an alternative, more stringent (tight) modeling protocol to avoid them. In addition to providing similar or better accuracy, this approach considerably reduces the DFT parameter calculation time (by a factor of 10 in the present case). We also show an example of how delayed or second-order mechanisms can then be added incrementally to the already built and tested, first-approximation model to achieve a highly predictive and comprehensive microkinetic model. We hope that this simple and robust microkinetic modeling protocol may contribute to the current efforts to establish new, more predictive computational methodologies for synthetic chemistry.
PB American Chemical Society
SN 2155-5435
YR 2019
FD 2019
LK https://uvadoc.uva.es/handle/10324/64847
UL https://uvadoc.uva.es/handle/10324/64847
LA eng
NO ACS Catal. 2019, 9, 6, 4804–4809
NO Producción Científica
DS UVaDOC
RD 22-nov-2024