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A W Kyri1, R Kunzmann1, G Schnakenburg1

  • 1Institut for Inorganic Chemistry of the Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhardt-Domagk-Strasse 1, 53121 Bonn, Germany. r.streubel@uni-bonn.de.

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Researchers report the first synthesis of an anionic frustrated Lewis pair (FLP) complex. This novel anionic FLP complex reacts readily with carbon dioxide (CO2) in a concerted manner.

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Area of Science:

  • Organometallic chemistry
  • Main group chemistry
  • Lewis pair chemistry

Background:

  • Frustrated Lewis pairs (FLPs) are reactive species formed from Lewis acids and bases that do not associate.
  • While FLP chemistry is well-researched, anionic FLPs and their complexes remain unexplored.
  • This knowledge gap limits the understanding of FLP reactivity and applications.

Purpose of the Study:

  • To synthesize and characterize the first monomolecular anionic FLP complex.
  • To investigate the reactivity of this novel anionic FLP complex.
  • To expand the scope of FLP chemistry into anionic systems.

Main Methods:

  • Synthesis of a tungsten-based precursor complex containing a silylated phosphine ligand.
  • Reaction of the precursor with dicyclohexylboron chloride (Cy2BCl).
  • Deprotonation using potassium bis(trimethylsilyl)amide (KHMDS) to generate the anionic FLP complex.
  • Characterization of the resulting complex.

Main Results:

  • Successful synthesis and characterization of the first anionic FLP complex, [(OC)5W{(Me3Si)2HCP(H)OLi(12-crown-4)}].
  • The anionic FLP complex was formed via reaction with Cy2BCl and deprotonation with KHMDS.
  • The obtained anionic FLP complex demonstrated reactivity towards carbon dioxide (CO2).
  • CO2 activation occurred in a concerted manner with the anionic FLP complex.

Conclusions:

  • The first anionic FLP complex has been synthesized and characterized.
  • This discovery opens new avenues in FLP chemistry by introducing anionic systems.
  • The reactivity of the anionic FLP complex with CO2 suggests potential applications in small molecule activation and catalysis.