Mechanism of the Suzuki–Miyaura Cross-Coupling Reaction Mediated by [Pd(NHC)(allyl)Cl] Precatalysts

Handle URI:
http://hdl.handle.net/10754/625083
Title:
Mechanism of the Suzuki–Miyaura Cross-Coupling Reaction Mediated by [Pd(NHC)(allyl)Cl] Precatalysts
Authors:
Meconi, Giulia Magi; Vummaleti, Sai V. C. ( 0000-0001-7276-2475 ) ; Luque-Urrutia, Jesús Antonio; Belanzoni, Paola ( 0000-0002-1286-9294 ) ; Nolan, Steven P. ( 0000-0001-9024-2035 ) ; Jacobsen, Heiko ( 0000-0003-0721-8726 ) ; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Solà, Miquel ( 0000-0002-1917-7450 ) ; Poater, Albert ( 0000-0002-8997-2599 )
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-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.
KAUST Department:
KAUST Catalysis Center (KCC)
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.
Publisher:
American Chemical Society (ACS)
Journal:
Organometallics
KAUST Grant Number:
OSR-2015-CCF-1974-03
Issue Date:
24-May-2017
DOI:
10.1021/acs.organomet.7b00114
Type:
Article
ISSN:
0276-7333; 1520-6041
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.
Additional Links:
http://pubs.acs.org/doi/abs/10.1021/acs.organomet.7b00114
Appears in Collections:
Articles; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorMeconi, Giulia Magien
dc.contributor.authorVummaleti, Sai V. C.en
dc.contributor.authorLuque-Urrutia, Jesús Antonioen
dc.contributor.authorBelanzoni, Paolaen
dc.contributor.authorNolan, Steven P.en
dc.contributor.authorJacobsen, Heikoen
dc.contributor.authorCavallo, Luigien
dc.contributor.authorSolà, Miquelen
dc.contributor.authorPoater, Alberten
dc.date.accessioned2017-06-21T06:42:08Z-
dc.date.available2017-06-21T06:42:08Z-
dc.date.issued2017-05-24en
dc.identifier.citationMeconi 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.en
dc.identifier.issn0276-7333en
dc.identifier.issn1520-6041en
dc.identifier.doi10.1021/acs.organomet.7b00114en
dc.identifier.urihttp://hdl.handle.net/10754/625083-
dc.description.abstractDensity 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.en
dc.description.sponsorshipA.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.en
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/acs.organomet.7b00114en
dc.titleMechanism of the Suzuki–Miyaura Cross-Coupling Reaction Mediated by [Pd(NHC)(allyl)Cl] Precatalystsen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.identifier.journalOrganometallicsen
dc.contributor.institutionInstitut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, c/Maria Aurèlia Capmany 6, 17003 Girona, Catalonia, Spainen
dc.contributor.institutionDipartimento di Chimica, Biologia e Biotecnologie and Istituto di Scienze e Tecnologie Molecolari del CNR (CNR-ISTM), Università di Perugia, Via Elce di Sotto, 8, 06123 Perugia, Italyen
dc.contributor.institutionDepartment of Inorganic and Physical Chemistry, Universiteit Gent, Krijgslaan 281, S-3, B-9000 Ghent, Belgiumen
dc.contributor.institutionKemKom, 1215 Ursulines Avenue, New Orleans, Louisiana 70116, United Statesen
kaust.authorVummaleti, Sai V. C.en
kaust.authorCavallo, Luigien
kaust.grant.numberOSR-2015-CCF-1974-03en
All Items in KAUST are protected by copyright, with all rights reserved, unless otherwise indicated.