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Antimony(i) → Pd(ii) complexes with the (μ-Sb)Pd2 coordination framework.

Monika Kořenková1, Martin Hejda1, Robert Jirásko2

  • 1Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská 573, CZ - 532 10, Pardubice, Czech Republic. libor.dostal@upce.cz.

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This study details the synthesis of novel palladium-antimony complexes, revealing antimony(I) compounds as versatile ligands in organometallic chemistry. The research highlights the unique bridging capabilities of the ArSb ligand in palladium chemistry.

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Area of Science:

  • Organometallic Chemistry
  • Coordination Chemistry
  • Main Group Chemistry

Background:

  • Antimony(I) compounds are less explored as ligands in organometallic chemistry compared to other main group elements.
  • Understanding the coordination behavior of low-valent main group elements is crucial for developing new catalytic systems and materials.

Purpose of the Study:

  • To synthesize and characterize novel palladium complexes featuring an antimony(I) ligand.
  • To investigate the coordination modes and electronic properties of the antimony(I) ligand in palladium complexes.
  • To explore the reactivity of the antimony(I) ligand with different palladium precursors.

Main Methods:

  • Synthesis of unique palladium-antimony complexes using dimeric allyl palladium(II) precursors and an antimony(I) compound (ArSb).
  • Structural characterization using NMR spectroscopy, mass spectrometry, and single-crystal X-ray diffraction.
  • Computational studies employing DFT methods to analyze bonding.
  • 121Sb Mössbauer spectroscopy for electronic structure investigation.

Main Results:

  • Novel complexes with a bridging μ-ArSb moiety were successfully synthesized, demonstrating the ligand's ability to bridge two palladium centers.
  • The antimony(I) ligand exhibited versatile donor properties, acting as both a 4e and 2e donor depending on the reaction stoichiometry.
  • Structural and spectroscopic analyses confirmed the formation of stable palladium-antimony bonds and provided insights into electronic structures.

Conclusions:

  • The antimony(I) compound ArSb is a versatile ligand capable of forming unique bridging complexes with palladium(II).
  • This work expands the scope of main group element ligands in organometallic chemistry, offering new possibilities for catalyst design.
  • The study provides a comprehensive understanding of the structural, bonding, and electronic properties of these novel palladium-antimony complexes.