Oxidative addition of phenyl bromide to Pd(BINAP) vs Pd(BINAP)(amine). Evidence for addition to Pd(BINAP).
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.
Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107, USA.
Shashank
S
Shekhar
Per
P
Ryberg
John F
JF
Hartwig
D001555:Benzene Derivatives / Q000138:chemical synthesis* / Q000737:chemistry* / Q000493:pharmacokinetics; D001965:Bromides / Q000737:chemistry*; D002384:Catalysis; D015394:Molecular Structure; D009281:Naphthalenes / Q000737:chemistry* / Q000493:pharmacokinetics; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry* / Q000493:pharmacokinetics; D010084:Oxidation-Reduction; D010165:Palladium / Q000737:chemistry*; D013816:Thermodynamics
C406943:BINAP, 2-naphthol; D001555:Benzene Derivatives; D001965:Bromides; D009281:Naphthalenes; D009942:Organometallic Compounds; D010165:Palladium