EVIDENCE FOR THE LIGATION OF PALLADIUM(0) COMPLEXES BY ACETATE IONS -CONSEQUENCES ON THE MECHANISM OF THEIR OXIDATIVE ADDITION WITH PHENYLIODIDE AND PHPD(OAC)(PPH(3))(2) AS INTERMEDIATE IN THE HECK REACTION
C. Amatore et al., EVIDENCE FOR THE LIGATION OF PALLADIUM(0) COMPLEXES BY ACETATE IONS -CONSEQUENCES ON THE MECHANISM OF THEIR OXIDATIVE ADDITION WITH PHENYLIODIDE AND PHPD(OAC)(PPH(3))(2) AS INTERMEDIATE IN THE HECK REACTION, Organometallics, 14(12), 1995, pp. 5605-5614
Addition of acetate anions to solutions of Pd-0(PPh(3))(4) results in
the formation of anionic species in which the acetate ion coordinates
the palladium(0) center, Pd-0(PPh(3))(3)(OAc)(-), which is in equilibr
ium with the less ligated complex, Pd-0(PPh(3))(2)(OAc)(-). The latter
undergoes oxidative addition with phenyl iodide to afford a mixture o
f PhPdI(PPh(3))(2) and PhPd(OAc)-(PPh(3))(2). Acetate ions react with
PhPdI(PPh(3))(2) to afford PhPd(OAc)(PPh(3))(2). Mixtures ofPd(OAc)(2)
and nPPh(3) (n greater than or equal to 4), commonly used as catalyst
s in Heck reactions, afford a palladium(0) complex that is ligated by
one acetate ion, yielding the anionic species Pd-0(PPh(3))(3)(OAc)(-)
and Pd-0(PPh(3))(2)(OAc)(-). The latter reacts with phenyl iodide. How
ever, this reaction does not afford the expected PhPdI(PPh3)2 complex
but instead affords PhPd(OAc)(PPh(3))(2). Reaction of PhPd(OAc)(PPh(3)
)(2) with styrene results in the formation of stilbene, demonstrating
that PhPd(OAc)(PPh(3))2 is an intermediate in the Heck reaction.