Mononuclear Palladium(I) Aryl Complexes Perform Cross-Coupling Reactions with Organic Halides

Open AccessCCS ChemistryRESEARCH ARTICLES5 Aug 2024Mononuclear Palladium(I) Aryl Complexes Perform Cross-Coupling Reactions with Organic Halides Tianqi Xia, Linhong Long, Xuebing Leng, Hui Chen and Liang Deng Tianqi Xia , Linhong Long , Xuebing Leng , Hui Chen and Liang Deng Citation: CCS Chemistry. 2024;0:1–24https://doi.org/10.31635/ccschem.024.202404464 SectionsSupplemental MaterialAboutPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail Mononuclear Pd(I) species represent the least understood Pd intermediates in Pd-catalyzed reactions and isolable complexes of the type are exceedingly rare. Herein, we report the synthesis and characterization of mononuclear Pd(I) complexes bearing aryl ligands, namely [(IPr)Pd(ArTrip-R-p)] (ArTrip-R-p = 4-R-2,6-bis(2′,4′,6′-triisopropylphenyl)phenyl, R = H, CF3), as well as their reactions with organic halides. The Pd(I) aryl complexes were prepared from the reactions of [(IPr)PdCl2]2 with the corresponding aryl lithium salts and have been characterized by various spectroscopic methods. EPR spectroscopy and calculation studies suggest their Pd(I) nature. Reactivity studies using [(IPr)Pd(ArTrip-CF3-p)] as the representative revealed the capability of the Pd(I) aryl complex in activating the carbon-halogen bonds of organic iodide and benzyl halides. In the reactions with para-substituted benzyl bromides, C(aryl)-C(benzyl) cross-coupling products are formed in moderate to good yields. Kinetic studies, radical trapping experiments, and theoretical calculations point out that the cross-coupling products are likely formed from the sequential steps of stepwise oxidative addition reaction of Pd(I) aryl complex with benzyl bromide involving Pd(II) intermediate followed by reductive elimination reactions of the resulting Pd(III) intermediates. Download figure Download PowerPoint Previous articleNext article FiguresReferencesRelatedDetails Issue AssignmentNot Yet AssignedSupporting Information Copyright & Permissions© 2024 Chinese Chemical Society Downloaded 19 times PDF downloadLoading ...