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C-I-Selective Cross-Coupling Enabled by a Cationic Palladium Trimer.

Claudia J Diehl1, Thomas Scattolin1, Ulli Englert1

  • 1Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074, Aachen, Germany.

Angewandte Chemie (International Ed. in English)
|November 2, 2018
PubMed
Summary
This summary is machine-generated.

This study introduces a stable palladium trimer catalyst. This novel catalyst selectively activates C-I bonds over C-Br bonds in carbon-carbon bond formations, outperforming traditional palladium catalysts.

Keywords:
C−C bond formationchemoselectivitycross-couplingdensity functional calculationspalladium trimers

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Area of Science:

  • Organometallic Chemistry
  • Catalysis
  • Materials Science

Background:

  • Growing interest in synergistic effects of multiple metals in catalysis.
  • Limited knowledge beyond bimetallic systems in catalysis.
  • Need for catalysts with selective bond activation capabilities.

Purpose of the Study:

  • To develop a straightforward method for accessing an air-stable palladium trimer.
  • To investigate the catalytic reactivity of the palladium trimer, particularly its ability to differentiate C-I from C-Br bonds.
  • To provide experimental and computational evidence for the trimer's direct involvement in catalytic reactions.

Main Methods:

  • Synthesis of an air-stable palladium trimer.
  • Experimental studies on C-C bond formation reactions (arylation and alkylation) using polyhalogenated arenes.
  • Computational modeling to elucidate reaction mechanisms and transition states.
  • Characterization of catalytic performance compared to traditional palladium catalysts.

Main Results:

  • Successful synthesis of a stable palladium trimer.
  • Demonstrated selective activation of C-I bonds over C-Br bonds in C-C coupling reactions.
  • Observed superior performance of the palladium trimer compared to typical Pd0 and PdI-PdI catalysts.
  • Identification of the first transition state for bond activation by a palladium trimer, supporting direct trimer reactivity.

Conclusions:

  • The palladium trimer offers a unique catalytic capability for selective C-I bond activation.
  • Direct trimer reactivity is feasible and advantageous in specific catalytic transformations.
  • This work expands the understanding of multinuclear metal catalysis beyond bimetallic systems.