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Low-coordinate bismuth cations.

Ryan J Schwamm1, Benjamin M Day, Martyn P Coles

  • 1School of Chemical and Physical Sciences, Victoria University of Wellington , PO Box 600, Wellington, New Zealand.

Inorganic Chemistry
|March 19, 2014
PubMed
Summary
This summary is machine-generated.

Chloride abstraction from a bismuth compound using aluminum or gallium trichloride readily forms cationic bismuth species. Unexpectedly, reactions with boron reagents resulted in neutral bismuth compounds due to aryl/alkyl transfer.

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Area of Science:

  • Organometallic Chemistry
  • Main Group Chemistry
  • Coordination Chemistry

Background:

  • Diamido-bismuth compounds offer unique reactivity due to the electropositive nature of bismuth.
  • Exploring facile routes to cationic bismuth species is crucial for developing novel inorganic materials and catalysts.

Purpose of the Study:

  • To investigate the chloride abstraction reactions of a diamido-bismuth precursor with group 13 metal halides.
  • To characterize the resulting cationic bismuth species and explore their structural properties.
  • To examine the reactivity of the bismuth precursor with borate salts.

Main Methods:

  • Chloride abstraction reactions using MCl3 (M = Al, Ga).
  • Stoichiometric and substoichiometric reactions to form different cationic species.
  • Crystallographic analysis to determine the solid-state structures of the bismuth complexes.
  • Reactions with sodium tetraaryl/alkylborates and tetraaryl/alkylammonium salts.

Main Results:

  • Facile synthesis of tetrachlorometallate salts [Bi(Me2Si{NAr}2)][MCl4] and μ-chlorido bridged cations [{Bi(Me2Si{NAr}2)}2(μ-Cl)][MCl4].
  • Crystal structures reveal unusual coordination environments for bismuth, including formally two-coordinate and oligomeric species with Bi···Cl contacts.
  • Attempted synthesis of borate salts led to unexpected aryl/alkyl transfer from boron to bismuth, forming neutral compounds Bi(Me2Si{NAr}2)R.

Conclusions:

  • Chloride abstraction with MCl3 provides a versatile route to cationic bismuth complexes with diverse structures.
  • The reactivity of the diamido-bismuth precursor with boron reagents highlights a novel pathway for B-C bond cleavage and formation of neutral bismuth species.
  • These findings expand the synthetic toolbox for organobismuth chemistry and open avenues for new applications.