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Updated: Jan 19, 2026

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
Silylpalladium Cations Enable the Oxidative Addition of C(sp3)-O Bonds
Andreas L Wierschen1, Neyen Romano1, Stephen J Lee2
1Caudill Laboratories, Department of Chemistry , The University of North Carolina at Chapel Hill , Chapel Hill , North Carolina 27599-3290 , United States.
Abstract:
The synthesis and characterization of the room-temperature and solution-stable silylpalladium cations (PCy3)2Pd-SiR3+(C6F5)4B- (SiR3 = SiMe2Et, SiHEt2) and (Xantphos)Pd-SiR3+(BArf4) (SiR3 = SiMe2Et, SiHEt2; Xantphos = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; BArf4 = (3,5-(CF3)2C6H3)4B-) are reported. Spectroscopic and ligand addition experiments suggest that silylpalladium complexes of the type (PCy3)2Pd-SiR3+ are three-coordinate and T-shaped. Addition of dialkyl ethers to both the PCy3 and Xantphos-based silylpalladium cations resulted in the cleavage of C(sp3)-O bonds and the generation of cationic Pd-alkyl complexes. Mechanistically enabling is the ability of silylpalladium cations to behave as sources of both electrophilic silylium ions and nucleophilic LnPd(0).
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