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Silylpalladium Cations Enable the Oxidative Addition of C(sp3)-O Bonds.

著者 Wierschen AL , Romano N , Lee SJ , Gagné MR
J Am Chem Soc.2019 Sep 18 ; ():.
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The synthesis and characterization of the room temperature and solution stable silylpalladium cations [(PCy3)2PdSiR3+(C6F5)4B- (SiR3 = SiMe2Et, SiEt2H)] and [(Xantphos)PdSiR3+(BArf4) (SiR3 = SiMe2Et, SiEt2H; 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)2PdSiR3+ are 3-coordinate and T-shaped. Ad-dition 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 both sources of electrophilic silylium ions and nucleophilic LnPd(0).
PMID: 31532990 [PubMed - as supplied by publisher]
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