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Exploring Oxidation State-Dependent Selectivity in Polymerization of Cyclic Esters and Carbonates with Zinc(II) Complexes.
iScience ; 7: 120-131, 2018 Sep 28.
Artigo em Inglês | MEDLINE | ID: mdl-30267674
Neutral zinc alkoxide complexes show high activity toward the ring-opening polymerization of cyclic esters and carbonates, to generate biodegradable plastics applicable in several areas. Herein, we use a ferrocene-chelating heteroscorpionate complex in redox-switchable polymerization reactions, and we show that it is a moderately active catalyst for the ring-opening polymerization of L-lactide, ɛ-caprolactone, trimethylene carbonate, and δ-valerolactone. Uniquely for this type of catalyst, the oxidized complex has a similar polymerization activity as the corresponding reduced compound, but displays significantly different rates of reaction in the case of trimethylene carbonate and δ-valerolactone. Investigations of the oxidized compound suggest the presence of an organic radical rather than an Fe(III) complex. Electronic structure and density functional theory (DFT) calculations were performed to support the proposed electronic states of the catalytic complex and to help explain the observed reactivity differences. The catalyst was also compared with a monomeric phenoxide complex to show the influence of the phosphine-zinc interaction on catalytic properties.





Texto completo: Disponível Coleções: Bases de dados internacionais Base de dados: MEDLINE Idioma: Inglês Revista: IScience Ano de publicação: 2018 Tipo de documento: Artigo País de afiliação: Estados Unidos