Ghent University Academic Bibliography

Advanced

Mechanism of the Suzuki-Miyaura cross-coupling reaction mediated by [Pd(NHC)(allyl)Cl] precatalysts

Giulia Magi Meconi, Sai Vikrama Chaitanya Vummaleti, Jesús Antonio Luque-Urrutia, Paola Belanzoni, Steven Nolan UGent, Heiko Jacobsen, Luigi Cavallo, Miguel Solà and Albert Poater (2017) ORGANOMETALLICS. 36(11). p.2088-2095
abstract
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-Me-2 (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 (Delta G(double dagger) approximate to 30.0 kcal/mol) and of the high yields (approximate to 90%) observed in the case of [Pd]-C1-2-4 complexes (Delta G(double dagger) approximate to 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.
Please use this url to cite or link to this publication:
author
organization
year
type
journalArticle (original)
publication status
published
subject
keyword
N-HETEROCYCLIC CARBENE, ORTHO-SUBSTITUTED BIARYLS, PALLADIUM-CATALYZED AMINATION, ARYL CHLORIDES, ROOM-TEMPERATURE, (NHC)PD(ALLYL)CL NHC, ARYLBORONIC ACIDS, SUPPORTED PRECATALYSTS, OXIDATIVE-ADDITION, OLEFIN METATHESIS
journal title
ORGANOMETALLICS
Organometallics
volume
36
issue
11
pages
2088 - 2095
Web of Science type
Article
Web of Science id
000403387300007
ISSN
0276-7333
1520-6041
DOI
10.1021/acs.organomet.7b00114
language
English
UGent publication?
yes
classification
A1
copyright statement
I have transferred the copyright for this publication to the publisher
id
8536740
handle
http://hdl.handle.net/1854/LU-8536740
date created
2017-11-09 11:45:36
date last changed
2018-02-23 12:43:18
@article{8536740,
  abstract     = {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-Me-2 (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 (Delta G(double dagger) approximate to 30.0 kcal/mol) and of the high yields (approximate to 90\%) observed in the case of [Pd]-C1-2-4 complexes (Delta G(double dagger) approximate to 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.},
  author       = {Magi Meconi, Giulia and Vummaleti, Sai Vikrama Chaitanya and Antonio Luque-Urrutia, Jes{\'u}s and Belanzoni, Paola and Nolan, Steven and Jacobsen, Heiko and Cavallo, Luigi and Sol{\`a}, Miguel and Poater, Albert},
  issn         = {0276-7333},
  journal      = {ORGANOMETALLICS},
  keyword      = {N-HETEROCYCLIC CARBENE,ORTHO-SUBSTITUTED BIARYLS,PALLADIUM-CATALYZED AMINATION,ARYL CHLORIDES,ROOM-TEMPERATURE,(NHC)PD(ALLYL)CL NHC,ARYLBORONIC ACIDS,SUPPORTED PRECATALYSTS,OXIDATIVE-ADDITION,OLEFIN METATHESIS},
  language     = {eng},
  number       = {11},
  pages        = {2088--2095},
  title        = {Mechanism of the Suzuki-Miyaura cross-coupling reaction mediated by [Pd(NHC)(allyl)Cl] precatalysts},
  url          = {http://dx.doi.org/10.1021/acs.organomet.7b00114},
  volume       = {36},
  year         = {2017},
}

Chicago
Magi Meconi, Giulia, Sai Vikrama Chaitanya Vummaleti, Jesús Antonio Luque-Urrutia, Paola Belanzoni, Steven Nolan, Heiko Jacobsen, Luigi Cavallo, Miguel Solà, and Albert Poater. 2017. “Mechanism of the Suzuki-Miyaura Cross-coupling Reaction Mediated by [Pd(NHC)(allyl)Cl] Precatalysts.” Organometallics 36 (11): 2088–2095.
APA
Magi Meconi, G., Vummaleti, S. V. C., Antonio Luque-Urrutia, J., Belanzoni, P., Nolan, S., Jacobsen, H., Cavallo, L., et al. (2017). Mechanism of the Suzuki-Miyaura cross-coupling reaction mediated by [Pd(NHC)(allyl)Cl] precatalysts. ORGANOMETALLICS, 36(11), 2088–2095.
Vancouver
1.
Magi Meconi G, Vummaleti SVC, Antonio Luque-Urrutia J, Belanzoni P, Nolan S, Jacobsen H, et al. Mechanism of the Suzuki-Miyaura cross-coupling reaction mediated by [Pd(NHC)(allyl)Cl] precatalysts. ORGANOMETALLICS. 2017;36(11):2088–95.
MLA
Magi Meconi, Giulia, Sai Vikrama Chaitanya Vummaleti, Jesús Antonio Luque-Urrutia, et al. “Mechanism of the Suzuki-Miyaura Cross-coupling Reaction Mediated by [Pd(NHC)(allyl)Cl] Precatalysts.” ORGANOMETALLICS 36.11 (2017): 2088–2095. Print.