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dc.contributor.authorZhou, Tongliang
dc.contributor.authorMa, Siyue
dc.contributor.authorNahra, Fady
dc.contributor.authorObled, Alan M C
dc.contributor.authorPoater, Albert
dc.contributor.authorCavallo, Luigi
dc.contributor.authorCazin, Catherine S. J.
dc.contributor.authorNolan, Steven P
dc.contributor.authorSzostak, Michal
dc.identifier.citationZhou, T., Ma, S., Nahra, F., Obled, A. M. C., Poater, A., Cavallo, L., … Szostak, M. (2020). [Pd(NHC)(μ-Cl)Cl]2: Versatile and Highly Reactive Complexes for Cross-Coupling Reactions that Avoid Formation of Inactive Pd(I) Off-Cycle Products. iScience, 23(8), 101377. doi:10.1016/j.isci.2020.101377
dc.description.abstractThe development of more reactive, general, easily accessible, and readily available Pd(II)-NHC precatalysts remains a key challenge in homogeneous catalysis. In this study, we establish air-stable NHC-Pd(II) chloro-dimers, [Pd(NHC)(μ-Cl)Cl]2, as the most reactive Pd(II)-NHC catalysts developed to date. Most crucially, compared with [Pd(NHC)(allyl)Cl] complexes, replacement of the allyl throw-away ligand with chloride allows for a more facile activation step, while effectively preventing the formation of off-cycle [Pd2(μ-allyl)(μ-Cl)(NHC)2] products. The utility is demonstrated via broad compatibility with amide cross-coupling, Suzuki cross-coupling, and the direct, late-stage functionalization of pharmaceuticals. Computational studies provide key insight into the NHC-Pd(II) chloro-dimer activation pathway. A facile synthesis of NHC-Pd(II) chloro-dimers in one-pot from NHC salts is reported. Considering the tremendous utility of Pd-catalyzed cross-coupling reactions and the overwhelming success of [Pd(NHC)(allyl)Cl] precatalysts, we believe that NHC-Pd(II) chloro-dimers, [Pd(NHC)(μ-Cl)Cl]2, should be considered as go-to precatalysts of choice in cross-coupling processes.
dc.description.sponsorshipWe thank Rutgers University (M.S.), the NSF (CAREER CHE-1650766, M.S.), and the NIH (1R35GM133326, M.S.) for financial support. The Bruker 500 MHz spectrometer used in this study was supported by the NSF-MRI grant (CHE-1229030). For work conducted in Belgium, S.P.N. and C.S.J.C. wish to thank the UGent BOF (starter and senior research grants). Umicore AG is thanked for gifts of materials. A.P. is a Serra Húnter Fellow and ICREA Academia Prize 2019 holder. A.P. thanks the Spanish MICINN for project PGC2018-097722-B-I00. T.Z. S.M. F.N. A.M.C.O. A.P. L.C. and C.S.J.C. performed the experiments. M.S. A.P. and S.P.N. wrote the manuscript and directed the project. All the authors discussed the results and commented on the manuscript. The authors declare no competing interests.
dc.publisherElsevier BV
dc.rightsThis is an open access article under the CC BY license.
dc.title[Pd(NHC)(μ-Cl)Cl]2: Versatile and Highly Reactive Complexes for Cross-Coupling Reactions that Avoid Formation of Inactive Pd(I) Off-Cycle Products.
dc.contributor.departmentChemical Science Program
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.eprint.versionPublisher's Version/PDF
dc.contributor.institutionDepartment of Chemistry, Rutgers University, 73 Warren Street, Newark, New Jersey 07102, USA
dc.contributor.institutionDepartment of Chemistry and Center for Sustainable Chemistry, Ghent University, Krijgslaan 281, S-3, B-9000 Ghent, Belgium
dc.contributor.institutionSeparation and Conversion Technology Unit, VITO (Flemish Institute for Technological Research), Boeretang 200, B-2400 Mol, Belgium
dc.contributor.institutionEaStCHEM School of Chemistry, University of St Andrews, St Andrews, KY16 9ST, UK
dc.contributor.institutionInstitut de Quimica Computacional i Catalisi and Departament de Quimica, Universitat de Girona, c/ Maria Aurelia Capmany 69, Campus Montilivi, 17003 Girona, Catalonia, Spain
kaust.personCavallo, Luigi

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