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Related Experiment Videos

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

Sebastian Kozuch1, Sason Shaik, Anny Jutand

  • 1Department of Organic Chemistry and Lise Meitner-Minerva Center for Computational Quantum Chemistry, Givat Ram Campus, Jerusalem 91904, Israel.

Chemistry (Weinheim an Der Bergstrasse, Germany)
|June 24, 2004
PubMed
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This study confirms the existence of tricoordinate, anionic zero-valent palladium complexes, crucial for palladium-catalyzed Heck and cross-coupling reactions. Computational analysis reveals their stability and distinct properties compared to dicoordinate species.

Area of Science:

  • Organometallic Chemistry
  • Computational Chemistry
  • Catalysis

Background:

  • Palladium-catalyzed reactions, such as Heck and cross-coupling, are vital in organic synthesis.
  • The precise nature of active catalytic species, particularly anionic zero-valent palladium complexes, remains debated.
  • Understanding these intermediates is key to optimizing catalytic efficiency.

Purpose of the Study:

  • To computationally investigate the existence and stability of tricoordinate, anionic zero-valent palladium complexes.
  • To characterize the geometric and electronic properties of these postulated active species.
  • To elucidate the bonding mechanism and factors influencing the stability of palladium-ligand bonds.

Main Methods:

  • Density Functional Theory (DFT) calculations at the B3LYP/LACVP*(+)//B3LYP/LACVP* level were employed.

Related Experiment Videos

  • A range of monodentate ([Pd(PR(3))(2)X](-)) and bidentate ([Pd[Ph(2)P(CH(2))(n)Ph(2)P]X](-)) palladium complexes were studied.
  • Gas-phase and solvent (THF) calculations were performed to assess stability.

    • Main Results:

    • The existence of tricoordinate, anionic zero-valent palladium complexes was confirmed as distinct minima in both gas phase and THF.
    • Detailed geometric parameters and Pd--X(-) dissociation energies were provided for various complexes.
    • Distinct NMR and IR spectral features differentiate tri- and dicoordinate palladium(0) species.
    • An orbital interaction model successfully explained bonding and stability trends.

    Conclusions:

    • Tricoordinate, anionic zero-valent palladium complexes are stable and exist under relevant conditions.
    • The stability of these complexes is influenced by ligand substituents (R), halide/acetate (X), and bidentate ligand linker length.
    • This work provides fundamental insights into the mechanism of palladium-catalyzed reactions.