Exploring Oxidation State-Dependent Selectivity in Polymerization of Cyclic Esters and Carbonates with Zinc(II)Complexes
Abubekerov M, Vicek V, Wei J, Miehlich M, Quan SM, Meyer K, Neuhauser D, Diaconescul PL (2018)
Publication Type: Journal article
Publication year: 2018
Journal
Book Volume: 7
Pages Range: 120-131
DOI: 10.1016/j.isci.2018.08.020
Abstract
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.
Authors with CRIS profile
Matthias Miehlich
Lehrstuhl für Anorganische und Allgemeine Chemie
Karsten Meyer
Lehrstuhl für Anorganische und Allgemeine Chemie
Involved external institutions
United States (USA) (US)How to cite
APA:
Abubekerov, M., Vicek, V., Wei, J., Miehlich, M., Quan, S.M., Meyer, K.,... Diaconescul, P.L. (2018). Exploring Oxidation State-Dependent Selectivity in Polymerization of Cyclic Esters and Carbonates with Zinc(II)Complexes. iScience, 7, 120-131. https://doi.org/10.1016/j.isci.2018.08.020
MLA:
Abubekerov, Mark, et al. "Exploring Oxidation State-Dependent Selectivity in Polymerization of Cyclic Esters and Carbonates with Zinc(II)Complexes." iScience 7 (2018): 120-131.
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