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Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of Phosphorus(I)
Published on: November 22, 2016
Oxidative addition of phenyl bromide to Pd(BINAP) vs Pd(BINAP)(amine). Evidence for addition to Pd(BINAP)
Shashank Shekhar1, Per Ryberg, John F Hartwig
1Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107, USA.
Abstract:
The rates of oxidative addition of phenyl bromide to [Pd(BINAP)2] have been measured in the presence and absence of added amine to assess a previous hypothesis that addition to [Pd(BINAP)(amine)] is faster than addition to [Pd(BINAP)]. These data show that addition to the amine complex is not faster than addition to [Pd(BINAP)]. Instead, they are consistent with oxidative addition, even in the presence of amine, to [Pd(BINAP)] as the major pathway. These data underscore the value of studying the stoichiometric reactions of isolated complexes when assessing the mechanism of a catalytic process.
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