Mechanism of the Suzuki–Miyaura Cross-Coupling Reaction Mediated by [Pd(NHC)(allyl)Cl] Precatalysts
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Meconi, Giulia MagiVummaleti, Sai V. C.

Luque-Urrutia, Jesús Antonio
Belanzoni, Paola

Nolan, Steven P.

Jacobsen, Heiko

Cavallo, Luigi

Solà, Miquel

Poater, Albert

KAUST Department
Chemical Science ProgramKAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
KAUST Grant Number
OSR-2015-CCF-1974-03Date
2017-05-24Online Publication Date
2017-05-24Print Publication Date
2017-06-12Embargo End Date
2018-05-24Permanent link to this record
http://hdl.handle.net/10754/625104
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Density functional theory calculations have been used to investigate the activation mechanism for the precatalyst series [Pd]-X-1–4 derived from [Pd(IPr)(R-allyl)X] species by substitutions at the terminal position of the allyl moiety ([Pd] = Pd(IPr); R = H (1), Me (2), gem-Me2 (3), Ph (4), X = Cl, Br). Next, we have investigated the Suzuki–Miyaura cross-coupling reaction for the active catalyst species IPr-Pd(0) using 4-chlorotoluene and phenylboronic acid as substrates and isopropyl alcohol as a solvent. Our theoretical findings predict an upper barrier trend, corresponding to the activation mechanism for the [Pd]-Cl-1–4 series, in good agreement with the experiments. They indeed provide a quantitative explanation of the low yield (12%) displayed by [Pd]-Cl-1 species (ΔG⧧ ≈ 30.0 kcal/mol) and of the high yields (≈90%) observed in the case of [Pd]-Cl-2–4 complexes (ΔG⧧ ≈ 20.0 kcal/mol). Additionally, the studied Suzuki–Miyaura reaction involving the IPr-Pd(0) species is calculated to be thermodynamically favorable and kinetically facile. Similar investigations for the [Pd]-Br-1–4 series, derived from [Pd(IPr)(R-allyl)Br], indicate that the oxidative addition step for IPr-Pd(0)-mediated catalysis with 4-bromotoluene is kinetically more favored than that with 4-chlorotoluene. Finally, we have explored the potential of Ni-based complexes [Ni((IPr)(R-allyl)X] (X = Cl, Br) as Suzuki–Miyaura reaction catalysts. Apart from a less endergonic reaction energy profile for both precatalyst activation and catalytic cycle, a steep increase in the predicted upper energy barriers (by 2.0–15.0 kcal/mol) is calculated in the activation mechanism for the [Ni]-X-1–4 series compared to the [Pd]-X-1–4 series. Overall, these results suggest that Ni-based precatalysts are expected to be less active than the Pd-based precatalysts for the studied Suzuki–Miyaura reaction.Citation
Meconi GM, Vummaleti SVC, Luque-Urrutia JA, Belanzoni P, Nolan SP, et al. (2017) Mechanism of the Suzuki–Miyaura Cross-Coupling Reaction Mediated by [Pd(NHC)(allyl)Cl] Precatalysts. Organometallics 36: 2088–2095. Available: http://dx.doi.org/10.1021/acs.organomet.7b00114.Sponsors
A.P. thanks the Spanish MINECO for a project CTQ2014-59832-JIN. M.S. thanks EU for a FEDER fund (UNGI08-4E-003), the Generalitat de Catalunya for project 2014SGR931 and ICREA Academia 2014 prize, and MINECO of Spain through project CTQ2014-54306-P. G.M.M. thanks LLP/Erasmus Student Placement Programme (A.A. 2012/2013) for funding. S.P.N. acknowledges the ERC for support of this work. This publication is based upon work supported by the King Abdullah University of Science and Technology (KAUST) Office of Sponsored Research (OSR) under Award No. OSR-2015-CCF-1974-03. We thank the referees for helpful comments and suggestions.Publisher
American Chemical Society (ACS)Journal
OrganometallicsAdditional Links
http://pubs.acs.org/doi/abs/10.1021/acs.organomet.7b00114https://dugi-doc.udg.edu/bitstream/10256/14359/1/AM-ReactionMechanism.pdf
ae974a485f413a2113503eed53cd6c53
10.1021/acs.organomet.7b00114