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• W2045010983 endingPage "81" @default.
• W2045010983 startingPage "79" @default.
• W2045010983 abstract "We report the isolation and reactivity of a series of ligandless, anionic arylpalladium complexes of the general structure [Pd(Ar)Br(2)](2)(2-) by the reaction of ((t)Bu(3)P)Pd(Ar)(Br) and bromide. These anionic complexes insert olefins at room temperature, and these fast insertions indicate that the anionic complexes are kinetically competent to be intermediates in Heck-Mizoroki reactions conducted under ligandless conditions (lacking added dative ligand). Kinetic studies showed that the anionic complexes insert olefins much faster than the corresponding neutral, P(t-Bu)(3)-ligated complexes. Addition of halide to the reaction of the neutral complex ((t)Bu(3)P)Pd(Ar)(Br) and styrene led to a significant rate acceleration, suggesting that the anionic complex forms rapidly and reversibly in situ from the neutral species prior to migratory insertion. These data, along with studies on the regioselectivity for reaction of aryl halides with butyl vinyl ether in the presence of the different starting catalysts, are consistent with the intermediacy of the same anionic, arylpalladium intermediates in Heck reactions catalyzed by palladium complexes containing bulky trialkylphosphine ligands as in reactions conducted under ligandless conditions." @default.
• W2045010983 created "2016-06-24" @default.
• W2045010983 creator A5051737534 @default.
• W2045010983 creator A5088865204 @default.
• W2045010983 date "2009-12-16" @default.
• W2045010983 modified "2023-10-08" @default.
• W2045010983 title "Ligandless, Anionic, Arylpalladium Halide Intermediates in the Heck Reaction" @default.
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• W2045010983 doi "https://doi.org/10.1021/ja909306f" @default.
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• W2045010983 hasPublicationYear "2009" @default.
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