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Mono-cyclononatetraenyl lanthanide complexes.

Luca Münzfeld1, Adrian Hauser1, Michael T Gamer1

  • 1Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstraße 15, Karlsruhe 76131, Germany. roesky@kit.edu.

Chemical Communications (Cambridge, England)
|July 6, 2023
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Summary
This summary is machine-generated.

Researchers synthesized novel half-sandwich complexes featuring the cyclononatetraenyl ligand for lanthanum and cerium. These complexes exhibit interesting reactivity, forming ionic species and polymeric structures upon solvent manipulation.

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Area of Science:

  • Organometallic Chemistry
  • Lanthanide Chemistry
  • Coordination Chemistry

Background:

  • Half-sandwich complexes offer unique structural and electronic properties.
  • Cyclononatetraenyl (Cnt) ligand is a less explored, highly unsaturated cyclic ligand.
  • Lanthanide complexes are crucial in catalysis and materials science.

Purpose of the Study:

  • To report the synthesis of the first half-sandwich complexes with the cyclononatetraenyl ligand.
  • To investigate the reactivity and structural diversity of these novel lanthanide complexes.
  • To explore the influence of solvent on the coordination environment and structure.

Main Methods:

  • Reaction of lanthanide borohydride precursors with potassium cyclononatetraenyl.
  • Solvation and solvent removal techniques to induce structural transformations.
  • Characterization of the resulting complexes using spectroscopic and crystallographic methods (implied).

Main Results:

  • Successful synthesis of [LnIII(η9-Cnt)(η3-BH4)2(thf)] (Ln = La, Ce) complexes.
  • Demonstration of reversible Cnt ring decoordination upon further solvation with tetrahydrofuran (THF), forming ionic species.
  • Formation of a polymeric structure, [LaIII(μ-η2:η2-BH4)2(η3-BH4)(η9-Cnt)]n, upon removal of THF.

Conclusions:

  • The cyclononatetraenyl ligand can effectively stabilize lanthanide(III) ions in half-sandwich complexes.
  • The coordination chemistry of these complexes is sensitive to solvent, allowing for structural interconversion.
  • This work expands the scope of organolanthanide chemistry and introduces new synthetic pathways.