C–H bond activation via concerted metalation–deprotonation at a palladium(iii) center

Bailey S. Bouley, Fengzhi Tang, Dae Young Bae, Liviu M. Mirica

Research output: Contribution to journalArticlepeer-review


Herein we report the direct observation of C–H bond activation at an isolated mononuclear Pd(III) center. The oxidation of the Pd(II) complex (MeN4)PdII(neophyl)Cl (neophyl = –CH2C(CH3)2Ph; MeN4 = N,N′-dimethyl-2,11-diaza[3.3](2,6)pyridinophane) using the mild oxidant ferrocenium hexafluorophosphate (FcPF6) yields the stable Pd(III) complex [(MeN4)PdIII(neophyl)Cl]PF6. Upon the addition of an acetate source, [(MeN4)PdIII(neophyl)Cl]PF6 undergoes Csp2–H bond activation to yield the cyclometalated product [(MeN4)PdIII(cycloneophyl)]PF6. This metalacycle can be independently prepared, allowing for a complete characterization of both the starting and final Pd(III) complexes. The C–H activation step can be monitored directly by EPR and UV-Vis spectroscopies, and kinetic isotope effect (KIE) studies suggest that either a pre-association step such as an agostic interaction may be rate limiting, or that the C–H activation is partially rate-limiting in conjunction with ligand rearrangement. Density functional theory calculations support that the reaction proceeds through a κ3 ligand coordination and that the flexible ligand structure is important for this transformation. Overall, this study represents the first example of discrete C–H bond activation occurring at a Pd(III) center through a concerted metalation–deprotonation mechanism, akin to that observed for Pd(II) and Pd(IV) centers.
Original languageEnglish (US)
Pages (from-to)3800-3808
Number of pages9
JournalChemical Science
Issue number14
Early online dateMar 13 2023
StatePublished - Mar 13 2023


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