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Controlled Photoredox Ring-Opening Polymerization of O-Carboxyanhydrides Mediated by Ni/Zn Complexes
Published on: November 21, 2017
Ring-opening polymerization of cyclic esters by phenoxy-thioether complexes derived from biocompatible metals.
Alessia Pilone1, Marina Lamberti, Mina Mazzeo
1Department of Chemistry and Biology, University of Salerno, I-84084, via Ponte don Melillo, Fisciano, Salerno, Italy. mlamberti@unisa.it mmazzeo@unisa.it.
Novel magnesium and zinc complexes with phenoxy-thioether ligands were synthesized. These complexes, particularly magnesium-based ones, show excellent catalytic activity and control in cyclic ester ring-opening polymerization (ROP).
Area of Science:
- Organometallic Chemistry
- Polymer Chemistry
- Catalysis
Background:
- Development of efficient catalysts for ring-opening polymerization (ROP) is crucial for producing biodegradable polymers.
- Phenoxy-thioether ligands offer unique coordination environments for metal complexes.
Purpose of the Study:
- To synthesize and characterize novel magnesium(II) and zinc(II) complexes supported by phenoxy-thioether ligands.
- To evaluate the catalytic performance of these complexes in the ring-opening polymerization of cyclic esters.
Main Methods:
- Synthesis of novel Mg(II) and Zn(II) complexes using various precursors and ligands.
- Characterization using techniques such as NMR spectroscopy and Diffusion Ordered SpectroscopY (DOSY).
- Evaluation of catalytic activity in ring-opening polymerization of ε-caprolactone and lactide.
Main Results:
- Successfully synthesized and characterized six novel Mg(II) and Zn(II) complexes.
- Variable temperature NMR and DOSY experiments indicated the dimeric nature of the complexes in solution.
- All synthesized complexes demonstrated catalytic activity in ROP.
- Magnesium complexes exhibited superior performance in terms of activity and control over molecular weights and distributions for ε-caprolactone and lactide ROP.
Conclusions:
- The novel phenoxy-thioether supported Mg(II) and Zn(II) complexes are effective catalysts for ROP.
- Magnesium complexes display enhanced catalytic properties, making them promising for biodegradable polymer synthesis.
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