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Dinucleating Amino-Phenolate Platform for Zinc Catalysts: Impact on Lactide Polymerization.

Shazia Soobrattee1, Xiaofang Zhai1, Kudzanai Nyamayaro1

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Inorganic Chemistry
|April 1, 2020
PubMed
Summary

New dinucleating ligands with zinc complexes show promise for catalyzing lactide polymerization. Trinuclear zinc alkyl catalysts offer enhanced control and reproducibility in this process.

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Area of Science:

  • Coordination Chemistry
  • Polymerization Catalysis
  • Organometallic Chemistry

Background:

  • Dinucleating ligands are crucial for developing cooperative bimetallic catalysts.
  • Zinc complexes are versatile catalysts for various organic transformations.
  • Lactide polymerization is a key process for producing biodegradable polymers.

Purpose of the Study:

  • To synthesize and characterize novel imine- and amine-based dinucleating ligands with a bisphenol backbone.
  • To explore the coordination chemistry of these ligands with zinc, forming various zinc complexes.
  • To evaluate the catalytic activity of these zinc complexes in lactide ring-opening polymerization.

Main Methods:

  • Synthesis of imine- and amine-based dinucleating ligands.
  • Coordination of ligands with zinc precursors to form metal complexes.
  • Full characterization of resulting dinuclear and trinuclear zinc complexes using spectroscopic and analytical techniques.
  • Catalytic testing of zinc complexes in lactide ring-opening polymerization.

Main Results:

  • Successfully synthesized and characterized imine- and amine-based dinucleating ligands and their corresponding zinc complexes (alkyl, alkoxide, acetate, amide).
  • Demonstrated the ability of the ligand framework to support both dinuclear and trinuclear zinc complexes.
  • Amine-based complexes exhibited higher reactivity than imine-based analogues in lactide polymerization.
  • Trinuclear zinc alkyl species displayed remarkable control and reproducibility in lactide polymerization.
  • Observed that the formation of trinuclear clusters can influence the extent of bimetallic cooperation.

Conclusions:

  • The developed bisphenol-based dinucleating ligands effectively support diverse zinc complexes, including multinuclear species.
  • Zinc complexes derived from these ligands are active catalysts for lactide ring-opening polymerization.
  • Trinuclear zinc alkyl complexes offer superior control and reproducibility, highlighting the potential of multinuclear catalysis.
  • Ligand design plays a critical role in modulating catalytic activity and the extent of cooperative effects in zinc-catalyzed polymerization.