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Trimethylscandium.

Damir Barisic1, Dominic Diether1, Cäcilia Maichle-Mössmer1

  • 1Institut für Anorganische Chemie , Eberhard Karls Universität Tübingen , Auf der Morgenstelle 18 , 72076 Tübingen , Germany.

Journal of the American Chemical Society
|August 1, 2019
PubMed
Summary
This summary is machine-generated.

A novel scandium tetramethylaluminate complex was synthesized and characterized. This complex, [Sc(AlMe4)3], shows unique reactivity and serves as a precursor for scandium methyl complexes and isoprene polymerization.

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Area of Science:

  • Organometallic Chemistry
  • Coordination Chemistry
  • Polymer Chemistry

Background:

  • Scandium complexes with aluminum alkyl ligands are not well-understood.
  • Tetramethylaluminate ligands offer unique electronic and steric properties.
  • Developing new precursors for polymerization catalysts is of significant interest.

Purpose of the Study:

  • To synthesize and characterize a novel homoleptic tetramethylaluminate scandium complex.
  • To investigate the reactivity and decomposition pathways of the new complex.
  • To explore the potential of scandium-aluminum complexes as polymerization catalysts.

Main Methods:

  • Synthesis of [Sc(AlMe4)3] from [Li3ScMe6(thf)1.2] and AlMe3 at low temperatures.
  • Cocrystallization and structural characterization of [Sc(AlMe4)3(Al2Me6)0.5].
  • Decomposition studies via C-H activation and NMR spectroscopy (45Sc NMR).
  • Derivatization with trimethyltriazacyclononane (Me3TACN) and salt metathesis reactions.
  • Isoprene polymerization using the cationized complex as a catalyst.

Main Results:

  • The novel homoleptic tetramethylaluminate complex [Sc(AlMe4)3] was successfully synthesized.
  • Decomposition pathways involving C-H activation led to mixed methyl/methylidene complexes.
  • Scandium methyl complexes, including [(Me3TACN)ScMe3], were formed and characterized.
  • Half-sandwich and sandwich complexes like [Cp*Sc(AlMe4)2] and [Cp*2Sc(AlMe4)] were obtained.
  • 45Sc NMR spectroscopy confirmed the presence of [ScMe3] and indicated significant deshielding.
  • The cationized complex catalyzed isoprene polymerization with high yield and cis-1,4-polyisoprene content.

Conclusions:

  • The synthesis of [Sc(AlMe4)3] expands the known organoscandium chemistry.
  • The complex exhibits rich reactivity, including C-H activation and ligand exchange.
  • Scandium-aluminum complexes show promise as catalysts for stereoselective isoprene polymerization.