Metadynamics simulations of R–NHC reductive elimination in intermediate palladium complexes of cross-coupling and Mizoroki–Heck reactions Full article
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Mendeleev Communications
ISSN: 1364-551X , E-ISSN: 0959-9436 |
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| Output data | Year: 2023, Volume: 33, Number: 2, Pages: 153-156 Pages count : 4 DOI: 10.1016/j.mencom.2023.02.002 | ||
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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).
Cite:
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. V.33. N2. P.153-156. DOI: 10.1016/j.mencom.2023.02.002 WOS Scopus OpenAlex
Metadynamics simulations of R–NHC reductive elimination in intermediate palladium complexes of cross-coupling and Mizoroki–Heck reactions
Mendeleev Communications. 2023. V.33. N2. P.153-156. DOI: 10.1016/j.mencom.2023.02.002 WOS Scopus OpenAlex
Identifiers:
| Web of science: | WOS:000982112500001 |
| Scopus: | 2-s2.0-85152255759 |
| OpenAlex: | W4362640990 |