The effect of chloride ions on the mechanism of the oxidative addition of cyclic allylic carbonates to Pd<sup>0</sup> complexes by formation of neutral [(η<sup>1</sup>-allyl)PdClL<inf>2</inf>] complexes

Thibault Cantat, Nicolas Agenet, Anny Jutand, Roser Pleixats, Marcial Moreno-Mañas

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Abstract

The reversible oxidative addition of a cyclic allylic carbonate cis-1 to palladium(0) complexes ligated by PPh3 is affected by chloride ions in DMF or chloroform. In the presence of chloride ions, the oxidative addition may become irreversible and the rate of isomerization of cis-1 to trans-1 is slowed down. This is a consequence of a slower isomerization of the cationic complex [(η3-allyl)Pd(PPh3)2]+ (cis-2+) to trans-2+ due to the formation of neutral [(η1-allyl)PdCl(PPh3)2] (cis-3/ trans-3) complexes. Such complexes are formed instead of the cationic cis-2+ and trans-2+ whatever the source of chloride ions, i.e., whether voluntarily added to the cationic complexes cis-2+ and trans-2 +, voluntarily added in the oxidative addition of cis-1 with Pd 0 complexes ligated to PPh3, or introduced in the dimeric complexes [(η3-allyl)Pd(μ-Cl)]2 (cis-5/trans-5). © Wiley-VCH Verlag GmbH & Co. KGaA, 2005.
Original languageEnglish
Pages (from-to)4277-4286
JournalEuropean Journal of Organic Chemistry
Issue number20
DOIs
Publication statusPublished - 14 Oct 2005

Keywords

  • Allyl ligands
  • Carbonates
  • Halides
  • Palladium
  • Reaction mechanisms

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