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Group 14 triple-decker cations.

Jamie N Jones1, Jennifer A Moore, Alan H Cowley

  • 1Department of Chemistry and Biochemistry, University of Texas at Austin, Austin, TX 78712, USA.

Dalton Transactions (Cambridge, England : 2003)
|November 29, 2005
PubMed
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New triple-decker tin and lead cations with decamethylcyclopentadienyl ligands were synthesized. These cations exhibit a cisoid arrangement of terminal ligands, contrasting with known anions, a difference explored via DFT calculations.

Area of Science:

  • Organometallic Chemistry
  • Main-Group Chemistry
  • Coordination Chemistry

Background:

  • Triple-decker complexes featuring main-group elements are of significant interest due to their unique electronic and structural properties.
  • Previous studies have characterized related triple-decker main-group anions with a transoid arrangement of terminal ligands.

Purpose of the Study:

  • To synthesize and structurally characterize novel triple-decker cations of tin and lead.
  • To investigate the conformational differences between these newly synthesized cations and previously known main-group triple-decker anions.

Main Methods:

  • Synthesis of triple-decker cations trans-[(Cp*Sn)(2)(mu-eta(5):eta(5)-Cp*)](+) and trans-[(Cp*Pb)(2)(mu-eta(5):eta(5)-Cp*)](+) as [B(C(6)F(5))(4)](-) salts.
  • Structural characterization using X-ray crystallography.

Related Experiment Videos

  • Density Functional Theory (DFT) calculations to probe conformational preferences.

    • Main Results:

    • Successful preparation and characterization of the target tin and lead triple-decker cations.
    • Observation that both cations adopt a cisoid arrangement of the terminal decamethylcyclopentadienyl (Cp*) ligands.
    • Comparison revealing a conformational difference: cisoid in cations versus transoid in known anions.

    Conclusions:

    • The synthesis expands the family of known triple-decker main-group complexes.
    • DFT calculations provide insights into the factors governing the observed cisoid conformation in the triple-decker cations.
    • Understanding these conformational preferences is crucial for designing and predicting the properties of related organometallic structures.