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Updated: Dec 20, 2025

Controlled Photoredox Ring-Opening Polymerization of O-Carboxyanhydrides Mediated by Ni/Zn Complexes
Published on: November 21, 2017
Bimetallic Zinc Catalysts for Ring-Opening Copolymerization Processes
Felipe de la Cruz-Martínez1, Marc Martínez de Sarasa Buchaca1, Javier Martínez1,2
1Departamento de Quı́mica Inorgánica, Orgánica y Bioquı́mica-Centro de Innovación en Quı́mica Avanzada (ORFEO-CINQA), Facultad de Ciencias y Tecnologı́as Quı́micas, Universidad de Castilla-La Mancha, 13071-Ciudad Real, Spain.
Abstract:
Novel bimetallic zinc acetate complexes supported by heteroscorpionate ligands have been developed for the ring-opening copolymerization of cyclohexene oxide and CO2 and the terpolymerization of cyclohexene oxide, phthalic anhydride, and CO2. Heteroscorpionate ligands precursors L-L were reacted with two equivalents of zinc acetate to afford the dinuclear zinc complexes [{Zn(κ3-bpzappe)}(μ-O2CCH3)3-{Zn(HO2CCH3)}] (1), [{Zn(κ3-bpzbdmape)}(μ-O2CCH3)3-{Zn(HO2CCH3)}] (2), and [{Zn(κ3-bpzbdeape)}(μ-O2CCH3)3{Zn(HO2CCH3)}] (3) in excellent yields. The molecular structure of these compounds was determined spectroscopically and confirmed by X-ray diffraction analysis. Zinc acetate complexes 1-3 were screened as catalysts for the copolymerization of cyclohexene oxide and CO2 to produce poly(cyclohexene)carbonate, and complex 3 was found to be the most active catalyst for this process in the absence of a cocatalyst. Furthermore, the terpolymerization of cyclohexene oxide, phthalic anhydride, and CO2 was studied using the combination of complex 3 and 4-dimethylaminopyridine as catalyst system yielding the corresponding polyester-polycarbonate materials.
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