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Rate and Mechanism of the Oxidative Addition of Benzoic Anhydride to Palladium(0) Complexes in DMF
Author(s) -
Jutand Anny,
Négri Serge,
de Vries Johannes G.
Publication year - 2002
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200207)2002:7<1711::aid-ejic1711>3.0.co;2-x
Subject(s) - chemistry , decarbonylation , oxidative addition , reactivity (psychology) , medicinal chemistry , palladium , reaction rate constant , cationic polymerization , denticity , trifluoromethanesulfonate , ligand (biochemistry) , photochemistry , stereochemistry , polymer chemistry , organic chemistry , catalysis , kinetics , metal , biochemistry , medicine , physics , alternative medicine , receptor , pathology , quantum mechanics
The rate constant of the oxidative addition of the benzoic anhydride (PhCO) 2 O to [Pd 0 (PPh 3 ) 4 ] has been determined in DMF and compared to that of phenyl halides and phenyl triflate. The following reactivity order has been established: PhI >> (PhCO) 2 O > PhOTf > PhBr. The oxidative addition of (PhCO) 2 O proceeds by activation of one C−O bond. Two acyl‐Pd II complexes are formed: a neutral complex trans ‐[(PhCO)Pd(OCOPh)(PPh 3 ) 2 ] and a cationic complex trans ‐[(PhCO)Pd S (PPh 3 ) 2 ] + ( S = DMF) showing that the decarbonylation process is highly endergonic. The exchange of PPh 3 by the bidentate ligand dppp does not favor the decarbonylation process.