Abstract
The stoichiometric addition of aryl and alkyl nitriles to the silylpalladium cation [(PCy3)2Pd–SiMe2Et+][(C6F5)4B–] (1) resulted in the cleavage of the nitrile C–CN bond and the formation of palladium–aryl and palladium–alkyl cations. Low-temperature experiments support a mechanism where silylpalladium cation 1 transfers silylium to nitrile, generating a silylnitrilium cation and the reduced, zerovalent complex Pd(PCy3)2. These two intermediates readily recombine at low temperatures to generate palladium–(N-silyl)iminoacyl complexes, which upon warming can undergo aryl/alkyl group migration from the iminoacyl ligand to the metal. Additional experiments show that palladium–(N-silyl)iminoacyl cations are potent sources of silylium, capable of cleaving the methyl C–O bond of an ether, while DFT calculations confirm the electrophilicity of the silyl moiety.
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