Active anionic zero-valent palladium catalysts: Characterization by density functional calculations

Sebastian Kozuch, Sason Shaik, Anny Jutand, Christian Amatore

Research output: Contribution to journalArticlepeer-review

102 Scopus citations


This works uses DFT (B3LYP/LACVP*+//B3LYP/LACVP* level) to ascertain the existence of the tricoordinate, anionic zero-valent palladium complexes that were postulated as the active species in the catalytic cycles of Pd-catalyzed Heck and cross-coupling reactions. The variety of complexes studied (1 and 2), include [Pd(PR3)2X] - species, in which R=H, Me, vinyl, and phenyl, and X=Cl, Br, I, AcO, and TFA, as well as bidentate complexes, [Pd{Ph2P(CH 2)nPh2P}X]-, in which X = Cl, AcO and n = 3-6. The study shows that these complexes exist as distinct minima in the gas phase as well as in THF. In addition, it provides geometric features and Pd-X- dissociation energies for all these complexes as well as some NMR and IR data, which show a clear distinction in these features between the tri- and dicoordinate Pd0 species. An orbital interaction model and perturbation theory arguments account for the bonding mechanism and rationalize all the trends in the stability of the Pd-X bond. These trends include the effects of variation of X, R, and the length of the linker in the bidentate ligands.

Original languageEnglish
Pages (from-to)3072-3080
Number of pages9
JournalChemistry - A European Journal
Issue number12
StatePublished - 21 Jun 2004
Externally publishedYes


  • Cross-coupling
  • Density functional calculations
  • Heck reaction
  • Ligand effects
  • Palladium


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