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SPANphos: trans-spanning diphosphines as cis chelating ligands!

Cristina Jiménez-Rodríguez1, Francesc X Roca, Carles Bo

  • 1Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 Tarragona, Spain.

Dalton Transactions (Cambridge, England : 2003)
|December 17, 2005
PubMed
Summary

SPANphos ligands, initially proposed as trans ligands, form cis chelating complexes with rhodium, palladium, and platinum. Computational studies reveal that while trans complexes are more stable, the cis conformation is enforced by ligands like norbornadiene.

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Area of Science:

  • Organometallic chemistry
  • Coordination chemistry
  • Computational chemistry

Background:

  • SPANphos ligands with a spirobichroman backbone were investigated.
  • These ligands were initially considered as putative trans ligands in metal complexes.

Purpose of the Study:

  • To synthesize and characterize novel metal complexes featuring SPANphos ligands.
  • To investigate the coordination behavior of SPANphos ligands with various transition metals.
  • To elucidate the conformational preferences of SPANphos and its complexes using computational methods.

Main Methods:

  • Synthesis of SPANphos ligands and their metal complexes ([Rh(nbd)(SPANphos)]BF(4), cyclooctadiene rhodium chloride derivatives).
  • X-ray crystallography for determining the structures of ligands and complexes.

Related Experiment Videos

  • Semiempirical AM1 and Density Functional Theory (DFT) calculations for conformational analysis and stability studies.

    • Main Results:

    • SPANphos ligands were found to act as cis chelating ligands in [Rh(nbd)(SPANphos)]BF(4) complexes, contrary to initial expectations.
    • Rhodium chloride derivatives with cyclooctadiene formed bimetallic complexes.
    • Crystal structures confirmed the coordination modes and molecular geometries.
    • Calculations indicated that the spirobichroman backbone can adopt conformations suitable for cis chelation.
    • DFT calculations showed that trans complexes of PdCl(2), PtCl(2), and Rh(CO)Cl with SPANphos are more stable than cis isomers by 4-10 kcal mol(-1).
    • The cis conformation of SPANphos in rhodium complexes is enforced by the presence of the cis chelating norbornadiene ligand.

    Conclusions:

    • SPANphos ligands exhibit versatile coordination behavior, capable of forming cis chelating complexes.
    • The conformational flexibility of the spirobichroman backbone influences the ligand's coordination mode.
    • While thermodynamically less stable, kinetic or steric factors, such as the presence of other cis ligands, can enforce the cis conformation in SPANphos complexes.