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Di-Zinc-Aryl Complexes: CO2 Insertions and Applications in Polymerisation Catalysis.
Charles Romain1, Jennifer A Garden2, Gemma Trott3
1Department of Chemistry, Imperial College London, London, SW7 2AZ, UK.
Chemistry (Weinheim an Der Bergstrasse, Germany)
|April 4, 2017
Summary
Two novel di-zinc-aryl complexes were synthesized and tested for reactivity. One complex readily activates carbon dioxide and catalyzes polymerizations, while the other shows no reaction, highlighting selective catalytic activity.
Area of Science:
- Coordination Chemistry
- Organometallic Chemistry
- Catalysis
Background:
- Macrocyclic ligands offer unique coordination environments for metal complexes.
- Di-zinc complexes are of interest for catalytic applications due to cooperative effects.
- Understanding metal-ligand interactions is crucial for designing selective catalysts.
Purpose of the Study:
- To synthesize and characterize new di-zinc-aryl complexes coordinated by a diphenol tetraamine macrocyclic ligand.
- To investigate the reactivity of these complexes with various monomers, including carbon dioxide and epoxides.
- To evaluate their catalytic performance in ring-opening polymerizations and copolymerizations.
Main Methods:
- Synthesis and full characterization of di-zinc-aryl complexes, including single-crystal X-ray diffraction.
- Experimental studies on the reactivity of complexes with monomers like carbon dioxide, cyclohexene oxide, and phthalic anhydride.
- Density functional theory (DFT) calculations to complement experimental findings.
Main Results:
- Two new di-zinc-aryl complexes, [LZn2Ph2] and [LZn2(C6F5)2], were successfully prepared and characterized.
- [LZn2Ph2] readily inserts carbon dioxide and exhibits catalytic activity in ring-opening copolymerization of cyclohexene oxide/carbon dioxide and ring-opening polymerization of rac-lactide and ε-caprolactone.
- [LZn2(C6F5)2] showed no reaction under the tested conditions, indicating selective reactivity.
Conclusions:
- The diphenol tetraamine macrocyclic ligand supports the formation of active di-zinc-aryl complexes.
- [LZn2Ph2] demonstrates significant potential as a catalyst for CO2 utilization and various ring-opening polymerizations.
- The electronic properties of the aryl groups influence the reactivity and catalytic performance of the di-zinc complexes.