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Kinetic Study and Nonlinear Phenomenon during the Copolymerization of CO 2 with meso ‐Epoxides Catalyzed by Various Bimetallic Co III Complexes
Author(s) -
Liu Ye,
Yu Yan,
Bao YuanYe,
Lu XiaoBing
Publication year - 2020
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.202000247
Subject(s) - bimetallic strip , copolymer , chemistry , reactivity (psychology) , catalysis , selectivity , epoxide , polymer chemistry , intramolecular force , cyclohexene oxide , reaction mechanism , organic chemistry , polymer , medicine , alternative medicine , pathology
The privileged salen ligands coordinated with a metal center have demonstrated their successful applications in many challenging reactions. Moreover, their relatively straightforward preparations and an ease of structural modifications are also very attractive. The Co III –salen complex has demonstrated to be one of the most efficient catalysts for the copolymerization of CO 2 with epoxides. Especially, the elaborate combination of two or more Co III –salen units into one single molecule may enforce an intramolecular, cooperative reaction pathway, resulting in enhanced reaction rates or/and higher selectivities. Otherwise, the reactivity and/or selectivity will be reduced, or some side reactions may occur. Herein, various bimetallic Co III complexes based on different linking groups are reported to bridge two salen planes, including flexible and rigid structures, together with their reactivities and selectivities toward copolymerization of CO 2 with meso ‐epoxides. The asymmetric depletion in copolymerization CO 2 with cyclohexene oxide mediated by monometallic Co III complex 2 is first observed, demonstrating the bimetallic mechanism; especially, the comparative kinetic measurements are performed as a function of reaction temperature to assess the activation barrier for production of copolymers for bi‐ and monometallic Co III complexes. This study is expected to be instructive and meaningful to design more efficient bimetallic catalyst and to improve the copolymerization selectivity.