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Unsolvated Al(C6F5)3: structural features and electronic interaction with ferrocene.

Jiawei Chen1, Eugene Y-X Chen

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The synthesis of unsolvated tris(pentafluorophenyl)aluminum, Al(C6F5)3, reveals a unique dimeric structure stabilized by Al-F interactions. This finding impacts understanding of its reactivity and sensitivity.

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Area of Science:

  • Organometallic Chemistry
  • Main Group Chemistry
  • Crystal Engineering

Background:

  • Tris(pentafluorophenyl)aluminum [Al(C6F5)3] is a Lewis acid with potential applications in catalysis.
  • Understanding its solid-state structure and reactivity is crucial for its practical use.
  • Previous studies have not fully characterized the unsolvated form.

Purpose of the Study:

  • To synthesize and structurally characterize unsolvated Al(C6F5)3.
  • To investigate the intermolecular interactions in the solid state.
  • To explore the complexation behavior of Al(C6F5)3 with ferrocene.

Main Methods:

  • Ligand exchange reaction between triethylaluminum [AlEt3] and tris(pentafluorophenyl)borane [B(C6F5)3].
  • Isolation and crystallization of unsolvated Al(C6F5)3.
  • Single-crystal X-ray diffraction analysis.
  • Spectroscopic studies of Al(C6F5)3-ferrocene adduct.

Main Results:

  • Formation and isolation of crystalline, unsolvated Al(C6F5)3.
  • X-ray diffraction revealed a dimeric structure with double Al-F interactions involving ortho-fluorine atoms.
  • The observed Al-F interactions differ from anticipated interactions with meta- and para-fluorines.
  • Complexation with ferrocene yields a stable adduct via η(1)-coordination of Al to a cyclopentadienyl ring.

Conclusions:

  • The dimeric structure of unsolvated Al(C6F5)3, stabilized by ortho-fluoro interactions, explains its sensitivity.
  • Al(C6F5)3 forms stable adducts with ferrocene through Lewis acid-base interactions.
  • This work provides fundamental insights into the structural chemistry and reactivity of a key organoaluminum compound.