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Metadynamics simulations of R-NHC reductive elimination in intermediate palladium complexes of cross-coupling and Mizoroki-Heck reactions

Alexander Yur'evich Kostyukovich 1
Alexander Yur'evich Kostyukovich
, 
Evgenii Georgievich Gordeev 1
Evgenii Georgievich Gordeev
, 
10.1016/j.mencom.2023.02.002
Published 2023-02-13
Communication , Volume 33, Issue 2, 153-156
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Kostyukovich A. Y., Gordeev E. G., Ananikov V. P. Metadynamics simulations of R-NHC reductive elimination in intermediate palladium complexes of cross-coupling and Mizoroki-Heck reactions // Mendeleev Communications. 2023. Vol. 33. No. 2. pp. 153-156.
GOST all authors (up to 50) Copy
Kostyukovich A. Y., Gordeev E. G., Ananikov V. P. Metadynamics simulations of R-NHC reductive elimination in intermediate palladium complexes of cross-coupling and Mizoroki-Heck reactions // Mendeleev Communications. 2023. Vol. 33. No. 2. pp. 153-156.
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TY - JOUR
DO - 10.1016/j.mencom.2023.02.002
UR - https://mendcomm.colab.ws/publications/10.1016/j.mencom.2023.02.002
TI - Metadynamics simulations of R-NHC reductive elimination in intermediate palladium complexes of cross-coupling and Mizoroki-Heck reactions
T2 - Mendeleev Communications
AU - Kostyukovich, Alexander Yur'evich
AU - Gordeev, Evgenii Georgievich
AU - Ananikov, Valentin Pavlovich
PY - 2023
DA - 2023/02/13
PB - Mendeleev Communications
SP - 153-156
IS - 2
VL - 33
ER -
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@article{2023_Kostyukovich,
author = {Alexander Yur'evich Kostyukovich and Evgenii Georgievich Gordeev and Valentin Pavlovich Ananikov},
title = {Metadynamics simulations of R-NHC reductive elimination in intermediate palladium complexes of cross-coupling and Mizoroki-Heck reactions},
journal = {Mendeleev Communications},
year = {2023},
volume = {33},
publisher = {Mendeleev Communications},
month = {Feb},
url = {https://mendcomm.colab.ws/publications/10.1016/j.mencom.2023.02.002},
number = {2},
pages = {153--156},
doi = {10.1016/j.mencom.2023.02.002}
}
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Kostyukovich, Alexander Yur'evich, et al. “Metadynamics simulations of R-NHC reductive elimination in intermediate palladium complexes of cross-coupling and Mizoroki-Heck reactions.” Mendeleev Communications, vol. 33, no. 2, Feb. 2023, pp. 153-156. https://mendcomm.colab.ws/publications/10.1016/j.mencom.2023.02.002.

Keywords

catalyst evolution
metadynamics.
molecular dynamics
palladium catalysis
R–NHC coupling
Reaction mechanism

Abstract

Exploring the free energy surface of the R-NHC coupling reaction in the key intermediates of the Mizoroki-Heck and cross-coupling catalytic cycles has been conducted by the methods of biased and unbiased molecular dynamics. Molecular dynamics simulations were carried out both in vacuum and in a polar solvent, with the following main observations on the influence of the media: (1) the solvent prevents the dissociation of the solvate ligand, so the R-NHC coupling proceeds in a four-coordination complex (rather than in a three-coordination one, as in the case of a gas-phase reaction); (2) in the condensed phase, the potential barrier of the reaction is significantly higher compared to the same process in vacuum (17.7 vs. 21.8 kcal mol-1); (3) polar solvent stabilizes the R-NHC coupling product. The reaction in a polar medium is exergonic (ΔG = −3.9 kcal mol-1), in contrast to the in vacuum modeling, where the process is endergonic (ΔG = 0.4 kcal mol-1).

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