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A computational mapping of the R–NHC coupling pathway – the key process in the evolution of Pd/NHC catalytic systems

Alexander Yur'evich Kostyukovich 1
Alexander Yur'evich Kostyukovich
, 
Evgenii Georgievich Gordeev 1
Evgenii Georgievich Gordeev
, 
10.1016/j.mencom.2022.09.001
Published 2022-09-05
Communication , Volume 32, Issue 5, 571-575
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Kostyukovich A. Y., Gordeev E. G., Ananikov V. P. A computational mapping of the R–NHC coupling pathway – the key process in the evolution of Pd/NHC catalytic systems // Mendeleev Communications. 2022. Vol. 32. No. 5. pp. 571-575.
GOST all authors (up to 50) Copy
Kostyukovich A. Y., Gordeev E. G., Ananikov V. P. A computational mapping of the R–NHC coupling pathway – the key process in the evolution of Pd/NHC catalytic systems // Mendeleev Communications. 2022. Vol. 32. No. 5. pp. 571-575.
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TY - JOUR
DO - 10.1016/j.mencom.2022.09.001
UR - https://mendcomm.colab.ws/publications/10.1016/j.mencom.2022.09.001
TI - A computational mapping of the R–NHC coupling pathway – the key process in the evolution of Pd/NHC catalytic systems
T2 - Mendeleev Communications
AU - Kostyukovich, Alexander Yur'evich
AU - Gordeev, Evgenii Georgievich
AU - Ananikov, Valentin Pavlovich
PY - 2022
DA - 2022/09/05
PB - Mendeleev Communications
SP - 571-575
IS - 5
VL - 32
ER -
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@article{2022_Kostyukovich,
author = {Alexander Yur'evich Kostyukovich and Evgenii Georgievich Gordeev and Valentin Pavlovich Ananikov},
title = {A computational mapping of the R–NHC coupling pathway – the key process in the evolution of Pd/NHC catalytic systems},
journal = {Mendeleev Communications},
year = {2022},
volume = {32},
publisher = {Mendeleev Communications},
month = {Sep},
url = {https://mendcomm.colab.ws/publications/10.1016/j.mencom.2022.09.001},
number = {5},
pages = {571--575},
doi = {10.1016/j.mencom.2022.09.001}
}
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Kostyukovich, Alexander Yur'evich, et al. “A computational mapping of the R–NHC coupling pathway – the key process in the evolution of Pd/NHC catalytic systems.” Mendeleev Communications, vol. 32, no. 5, Sep. 2022, pp. 571-575. https://mendcomm.colab.ws/publications/10.1016/j.mencom.2022.09.001.

Keywords

catalyst evolution
DFT calculations
palladium catalysis
R–NHC coupling
Reaction mechanism

Abstract

C–C coupling reactions are of great importance in metal-catalyzed synthetic transformations. Reductive elimination of two carbon centers is the key stage, which takes place in the metal coordination sphere. In the present study, we provide a detailed analysis of nonclassical R–NHC coupling in the model (NHC)Pdii(Ph)(X)(Solv) complex, which is a representative intermediate of the Mizoroki–Heck and cross-coupling reactions. This C–C bond formation stage proceeds as Ph ligand movement and insertion into the Pd–NHC bond, rather than classical C–C coupling. Based on the analysis by the quantum theory of atoms in molecules (QTAIM) of the reaction path structures, the atomic rearrangements and alterations in the electronic system during the R–NHC coupling process were characterized in detail.

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